6. POTENTIAL FOR HUMAN EXPOSURE

42
249 TIN AND TIN COMPOUNDS 6. POTENTIAL FOR HUMAN EXPOSURE 6.1 OVERVIEW Tin and organotin compounds have been identified in at least 214 and 8 sites, respectively, of the 1,662 hazardous waste sites that have been proposed for inclusion on the EPA National Priorities List (NPL) (HazDat 2004). However, the number of sites evaluated for tin and organotin compounds is not known. The frequency of these sites can be seen in Figures 6-1 and 6-2, respectively. All sites where tin and organotin compounds were found are located in the United States. Tin occurs naturally in the earth's crust with a concentration of approximately 2–3 ppm (Budavari 2001). Tin compounds are found in various environmental media in both inorganic and organic forms. Tin may be released to the environment from natural and anthropogenic sources. Tin is a component of many soils and inorganic tin compounds may be released in dusts from wind storms, roads, and agricultural activities. Releases of tin to environmental media may occur from the production and use of tin and tin compounds. Gases, dusts, and fumes containing tin may be released from smelting and refining processes, industrial uses of tin, waste incineration, and burning of fossil fuels (Byrd and Andreae 1986; Senesi et al. 1999; WHO 1980). In general, organotin compounds are released to the environment from anthropogenic sources; however, methyltin compounds can be produced in the environment by biomethylation of inorganic tin and can occur naturally (Fent 1996). Antifouling paints containing tributyltin are applied as a finish coat to the immersed sections of boats and floating structures. As the paint releases tributyltin into the water, it creates an environment that repels the organisms that may attach to the surface of submerged objects. Use of antifouling paints represents the major source of tributyltin into the coastal environment (Alzieu 1998). The use of tributyltin compounds as slimicides on masonry, disinfectants, and biocides for cooling systems, power station cooling towers, pulp and paper mills, breweries, leather processing, and textile mills (WHO 1990) may result in their release to the environment. Triphenyltin enters the environment directly from its use as a pesticide. To a lesser extent, organotin compounds may also enter the environment by leaching to soil and groundwater from consumer products containing organotin compounds disposed of in landfills (Fent 1996). Tin may exist in either divalent (Sn 2+ ) or tetravalent (Sn 4+ ) cationic (positively charged) ions at environmental conditions. Tin(II) dominates in reduced (oxygen-poor) water, and will readily precipitate as a sulfide (SnS) or as a hydroxide (Sn(OH) 2 ) in alkaline water. Tin(IV) readily hydrolyzes, and can precipitate as a hydroxide. In general, tin(IV) would be expected to be the only stable ionic species in the

Transcript of 6. POTENTIAL FOR HUMAN EXPOSURE

249 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

61 OVERVIEW

Tin and organotin compounds have been identified in at least 214 and 8 sites respectively of the

1662 hazardous waste sites that have been proposed for inclusion on the EPA National Priorities List

(NPL) (HazDat 2004) However the number of sites evaluated for tin and organotin compounds is not

known The frequency of these sites can be seen in Figures 6-1 and 6-2 respectively All sites where tin

and organotin compounds were found are located in the United States

Tin occurs naturally in the earths crust with a concentration of approximately 2ndash3 ppm (Budavari 2001)

Tin compounds are found in various environmental media in both inorganic and organic forms Tin may

be released to the environment from natural and anthropogenic sources Tin is a component of many soils

and inorganic tin compounds may be released in dusts from wind storms roads and agricultural

activities Releases of tin to environmental media may occur from the production and use of tin and tin

compounds Gases dusts and fumes containing tin may be released from smelting and refining

processes industrial uses of tin waste incineration and burning of fossil fuels (Byrd and Andreae 1986

Senesi et al 1999 WHO 1980) In general organotin compounds are released to the environment from

anthropogenic sources however methyltin compounds can be produced in the environment by

biomethylation of inorganic tin and can occur naturally (Fent 1996) Antifouling paints containing

tributyltin are applied as a finish coat to the immersed sections of boats and floating structures As the

paint releases tributyltin into the water it creates an environment that repels the organisms that may

attach to the surface of submerged objects Use of antifouling paints represents the major source of

tributyltin into the coastal environment (Alzieu 1998) The use of tributyltin compounds as slimicides on

masonry disinfectants and biocides for cooling systems power station cooling towers pulp and paper

mills breweries leather processing and textile mills (WHO 1990) may result in their release to the

environment Triphenyltin enters the environment directly from its use as a pesticide To a lesser extent

organotin compounds may also enter the environment by leaching to soil and groundwater from consumer

products containing organotin compounds disposed of in landfills (Fent 1996)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide In general tin(IV) would be expected to be the only stable ionic species in the

TIN AND TIN COMPOUNDS 250

6 POTENTIAL FOR HUMAN EXPOSURE

Figure 6-1 Frequency of NPL Sites with Tin Contamination

Frequency of NPL Sites

1-2 3-4 5-6 7-8 9-10 Derived from HazDat 2005 11-19

TIN AND TIN COMPOUNDS 251

6 POTENTIAL FOR HUMAN EXPOSURE

Figure 6-2 Frequency of NPL Sites with Organotin Contamination

Frequency of NPL Sites

1 3

Derived from HazDat 2005

252 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

weathering cycle (Wedepohl et al 1978) Tin in water may partition to soils and sediments Cations such

as Sn2+ and Sn4+ will generally be adsorbed by soils to some extent which reduces their mobility Tin is

generally regarded as being relatively immobile in the environment (Gerritse et al 1982 WHO 1980)

Organotin compounds are generally only sparingly soluble in water and are likely to partition to soils and

sediments Most commercially used organotin compounds are relatively immobile in environmental

media due to their low vapor pressures low water solubilities and high affinities for soil and organic

sediments (Blunden et al 1984) For example nearly all of the tributyltin found in the water column is

bound to suspended particles with a small portion associated with dissolved organic matter and organic

and inorganic ligands (Gadd 2000) Tributyltin that is associated with particles in the water column may

settle out which is an important process in its removal from the water column Tributyltin sorption

coefficients to sediments can range from 100 to 10000 (Anderson et al 2002) Degradation of organotin

compounds involves breaking the tin-carbon bond and can occur in the environment by ultraviolet (UV)

irradiation or biological or chemical cleavage (Blunden et al 1984) Rates of photodegradation and

biodegradation of organotins in water are dependent upon environmental conditions In sediment

organotins are generally persistent Organotin compounds may be significantly bioconcentrated by

aquatic organisms Cleavage of the tin-carbon bond by hydrolysis is not a significant environmental fate

process under environmental conditions (WHO 1990)

Occupational exposure to tin may be significant in some industrial environments Ambient environshy

mental levels of tin are generally quite low except in the vicinity of pollution sources Humans may be

exposed to tin by inhalation ingestion or dermal absorption However typical human exposure to tin is

primarily by ingestion of food Tin-lined cans used to package food constitute the most important

contribution to tin intake in the diet (Bieacutego et al 1999) While there is evidence that tin is essential for

the normal growth of rats there is no evidence that tin is essential for other animals including humans

(WHO 1980) Exposure to organotin compounds may occur by the ingestion of seafood and contact with

consumer products that contain organotin compounds Household commodities made up of polyurethane

plastic polymers and silicons contain butyltin concentrations in the parts per million range (Kannan et al

1999) Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in drinking

water in Canada where polyvinyl chloride (PVC) pipes containing these organotin compounds are used

in the distribution of drinking water (Sadiki and Williams 1996 1999 Sadiki et al 1996) Organotin

compounds were detected in household dust in the United Kingdom (Santillo et al 2003)

253 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

62 RELEASES TO THE ENVIRONMENT

The Toxics Release Inventory (TRI) data should be used with caution because only certain types of

facilities are required to report (EPA 1997) Manufacturing and processing facilities are required to report

information to the TRI only if they employ 10 or more full-time employees if their facility is classified

under Standard Industrial Classification (SIC) codes 20ndash39 and if their facility produces imports or

processes ge25000 pounds of any TRI chemical or otherwise uses gt10000 pounds of a TRI chemical in a

calendar year (EPA 1997)

There is no information on releases of tin and tin compounds from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997) However releases of tin to

environmental media may occur from the production and use of tin and tin compounds

Tin and organotin compounds have been identified in a variety of environmental media (air surface

water leachate groundwater soil and sediment) collected at 214 and 8 sites respectively of the

1662 current or former NPL hazardous waste sites (HazDat 2004)

621 Air

There is no information on releases of tin and tin compounds to the atmosphere from manufacturing and

processing facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in air collected at 6 of the 214 current or former NPL hazardous waste sites where

it was detected in some environmental media No organotin compounds were found in air at the eight

current or former NPL hazardous waste sites where organotin compounds were detected in some

environmental media (HazDat 2004)

Tin may be released to the atmosphere from both natural and anthropogenic sources Tin is a component

of many soils and may be released in dusts from wind storms roads and agricultural activities Gases

dusts and fumes containing tin may be released from smelting and refining processes industrial uses of

tin waste incineration and burning of fossil fuels (Byrd and Andreae 1986 Senesi et al 1999 WHO

1980) Davison et al (1974) reported that the tin content of airborne fly ash from coal-burning power

plants ranged from 7 to 19 microgg Worldwide emissions of tin to the atmosphere from coal and oil

combustion refuse incineration and coppernickel production facilities were estimated at 1470ndash

254 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

10810 metric tons in 1983 (Nriagu and Pacyna 1988) Organotin compounds may be released to air by

agricultural spraying volatilization antifouling paint sprays incineration of materials treated or stabilized

with organotin compounds and glass coating operations Incineration of organotin containing material is

unlikely to be a significant source of organotin compounds to air since these compounds will be

decomposed to inorganic tin during combustion (Blunden et al 1984) Releases of organotin compounds

to air are not significant due to their low vapor pressures and rapid photodegradation (Blunden et al 1984

Fent 1996)

622 Water

There is no information on releases of tin and tin compounds to water from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in groundwater and surface water at 78 and 36 sites respectively of the 214 NPL

hazardous waste sites where it was detected in some environmental media Organotin compounds were

found in surface water at one of the eight current or former NPL hazardous waste sites where they were

detected in some environmental media organotin compounds were not found in groundwater at these

sites (HazDat 2004)

Releases of tin to water may occur from industrial facilities smelting refining or using tin (WHO 1980)

Antifouling paints containing tributyltin are applied as a finish coat to the immersed sections of boats and

floating structures As the paint releases tributyltin into the water it creates an environment that repels

the organisms that may attach to the surface of submerged objects Use of antifouling paints represents

the major source of tributyltin into the coastal environment It has been estimated that one boat releases

1ndash10 microg tributyltincm2 of hull surface daily to ensure antifouling protection This corresponds to 02ndash

2 gday for a small sailboat and up to 50ndash500 gday for an average sized merchant ship (Alzieu 1998)

The use of triorganotin compounds as marine antifoulants has been restricted by the Organotin

Antifouling Paints Control Act (June 16 1988) which limits the type of vessel on which these paints can

be used and limits the use of tributyltin paints that have laboratory tested release rates of le4 microgcm2day

(Cardwell et al 1999a) Most industrialized countries in addition to the United States have adopted

similar restrictions on the use of tributyltin containing paints These countries include the United

Kingdom Canada France New Zealand Australia and the European Union (Birchenough et al 2002)

255 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Organotin compounds may also be released to water from overspray and land runoff from agricultural

applications industrial processes and leaching from organotin-stabilized polyvinyl chloride (PVC)

(Blunden et al 1984) The use of tributyltin compounds as slimicides on masonry disinfectants and

biocides for cooling systems power station cooling towers pulp and paper mills breweries leather

processing and textile mills may result in their release to the environment (WHO 1990) Triphenyltin

acetate and triphenyltin hydroxide are used as fungicides algicides and molluscicides (WHO 1999)

Timber treatment facilities can be as a significant source of tributyltin in freshwater systems from

seepage accidental spills and intentional releases Minor sources of organotin compounds in freshwater

can be seepage from landfill sites and agricultural runoff due to the use of contaminated sewage sludge or

organotin containing pesticides (Demora and Pelletier 1997) Monthly samples of influent effluent and

sludges were collected from July 1990 to January 1991 from sewage treatment plants in five Canadian

cities Monobutyltin was detected in all influent samples Dibutyl- and tributyltin were only detected

infrequently and octyltin species were not detected A significant reduction 40 on average in the

concentration of monomethyltin was found after passage through the sewage treatment plants due to

degradation and adsorption to sludge No butyltin or octyltin species were found in five landfill leachate

samples in southern Ontario Canada (Chau et al 1992)

623 Soil

There is no information on releases of tin and tin compounds to soil from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in soil at 121 sites and in sediment at 49 sites collected from 214 NPL hazardous

waste sites where it was detected in some environmental media Organotin compounds were found in

sediment and soil at four sites and one site respectively of the eight current or former NPL hazardous

waste sites where they were detected in some environmental media (HazDat 2004)

Tin may be released to soil from organotin pesticide usage and landfilling of tin-containing wastes

including used cans and organotin-containing plastics (WHO 1980) The application of pre-treated

municipal sludge and urban refuse as soil amendments may also introduce tin to soils Concentrations of

tin in sewage sludges from countries in Europe and North America ranged from 40 to 700 mgkg dry

weight Manures and poultry wastes contained tin at concentrations of 37ndash74 and 20ndash41 mgkg dry

weight respectively Other incidental point sources that may introduce tin to soil are corrosion of metal

objects and dispersion of metallic ores during transport (Senesi et al 1999) Organotin compounds may

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

TIN AND TIN COMPOUNDS 250

6 POTENTIAL FOR HUMAN EXPOSURE

Figure 6-1 Frequency of NPL Sites with Tin Contamination

Frequency of NPL Sites

1-2 3-4 5-6 7-8 9-10 Derived from HazDat 2005 11-19

TIN AND TIN COMPOUNDS 251

6 POTENTIAL FOR HUMAN EXPOSURE

Figure 6-2 Frequency of NPL Sites with Organotin Contamination

Frequency of NPL Sites

1 3

Derived from HazDat 2005

252 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

weathering cycle (Wedepohl et al 1978) Tin in water may partition to soils and sediments Cations such

as Sn2+ and Sn4+ will generally be adsorbed by soils to some extent which reduces their mobility Tin is

generally regarded as being relatively immobile in the environment (Gerritse et al 1982 WHO 1980)

Organotin compounds are generally only sparingly soluble in water and are likely to partition to soils and

sediments Most commercially used organotin compounds are relatively immobile in environmental

media due to their low vapor pressures low water solubilities and high affinities for soil and organic

sediments (Blunden et al 1984) For example nearly all of the tributyltin found in the water column is

bound to suspended particles with a small portion associated with dissolved organic matter and organic

and inorganic ligands (Gadd 2000) Tributyltin that is associated with particles in the water column may

settle out which is an important process in its removal from the water column Tributyltin sorption

coefficients to sediments can range from 100 to 10000 (Anderson et al 2002) Degradation of organotin

compounds involves breaking the tin-carbon bond and can occur in the environment by ultraviolet (UV)

irradiation or biological or chemical cleavage (Blunden et al 1984) Rates of photodegradation and

biodegradation of organotins in water are dependent upon environmental conditions In sediment

organotins are generally persistent Organotin compounds may be significantly bioconcentrated by

aquatic organisms Cleavage of the tin-carbon bond by hydrolysis is not a significant environmental fate

process under environmental conditions (WHO 1990)

Occupational exposure to tin may be significant in some industrial environments Ambient environshy

mental levels of tin are generally quite low except in the vicinity of pollution sources Humans may be

exposed to tin by inhalation ingestion or dermal absorption However typical human exposure to tin is

primarily by ingestion of food Tin-lined cans used to package food constitute the most important

contribution to tin intake in the diet (Bieacutego et al 1999) While there is evidence that tin is essential for

the normal growth of rats there is no evidence that tin is essential for other animals including humans

(WHO 1980) Exposure to organotin compounds may occur by the ingestion of seafood and contact with

consumer products that contain organotin compounds Household commodities made up of polyurethane

plastic polymers and silicons contain butyltin concentrations in the parts per million range (Kannan et al

1999) Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in drinking

water in Canada where polyvinyl chloride (PVC) pipes containing these organotin compounds are used

in the distribution of drinking water (Sadiki and Williams 1996 1999 Sadiki et al 1996) Organotin

compounds were detected in household dust in the United Kingdom (Santillo et al 2003)

253 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

62 RELEASES TO THE ENVIRONMENT

The Toxics Release Inventory (TRI) data should be used with caution because only certain types of

facilities are required to report (EPA 1997) Manufacturing and processing facilities are required to report

information to the TRI only if they employ 10 or more full-time employees if their facility is classified

under Standard Industrial Classification (SIC) codes 20ndash39 and if their facility produces imports or

processes ge25000 pounds of any TRI chemical or otherwise uses gt10000 pounds of a TRI chemical in a

calendar year (EPA 1997)

There is no information on releases of tin and tin compounds from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997) However releases of tin to

environmental media may occur from the production and use of tin and tin compounds

Tin and organotin compounds have been identified in a variety of environmental media (air surface

water leachate groundwater soil and sediment) collected at 214 and 8 sites respectively of the

1662 current or former NPL hazardous waste sites (HazDat 2004)

621 Air

There is no information on releases of tin and tin compounds to the atmosphere from manufacturing and

processing facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in air collected at 6 of the 214 current or former NPL hazardous waste sites where

it was detected in some environmental media No organotin compounds were found in air at the eight

current or former NPL hazardous waste sites where organotin compounds were detected in some

environmental media (HazDat 2004)

Tin may be released to the atmosphere from both natural and anthropogenic sources Tin is a component

of many soils and may be released in dusts from wind storms roads and agricultural activities Gases

dusts and fumes containing tin may be released from smelting and refining processes industrial uses of

tin waste incineration and burning of fossil fuels (Byrd and Andreae 1986 Senesi et al 1999 WHO

1980) Davison et al (1974) reported that the tin content of airborne fly ash from coal-burning power

plants ranged from 7 to 19 microgg Worldwide emissions of tin to the atmosphere from coal and oil

combustion refuse incineration and coppernickel production facilities were estimated at 1470ndash

254 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

10810 metric tons in 1983 (Nriagu and Pacyna 1988) Organotin compounds may be released to air by

agricultural spraying volatilization antifouling paint sprays incineration of materials treated or stabilized

with organotin compounds and glass coating operations Incineration of organotin containing material is

unlikely to be a significant source of organotin compounds to air since these compounds will be

decomposed to inorganic tin during combustion (Blunden et al 1984) Releases of organotin compounds

to air are not significant due to their low vapor pressures and rapid photodegradation (Blunden et al 1984

Fent 1996)

622 Water

There is no information on releases of tin and tin compounds to water from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in groundwater and surface water at 78 and 36 sites respectively of the 214 NPL

hazardous waste sites where it was detected in some environmental media Organotin compounds were

found in surface water at one of the eight current or former NPL hazardous waste sites where they were

detected in some environmental media organotin compounds were not found in groundwater at these

sites (HazDat 2004)

Releases of tin to water may occur from industrial facilities smelting refining or using tin (WHO 1980)

Antifouling paints containing tributyltin are applied as a finish coat to the immersed sections of boats and

floating structures As the paint releases tributyltin into the water it creates an environment that repels

the organisms that may attach to the surface of submerged objects Use of antifouling paints represents

the major source of tributyltin into the coastal environment It has been estimated that one boat releases

1ndash10 microg tributyltincm2 of hull surface daily to ensure antifouling protection This corresponds to 02ndash

2 gday for a small sailboat and up to 50ndash500 gday for an average sized merchant ship (Alzieu 1998)

The use of triorganotin compounds as marine antifoulants has been restricted by the Organotin

Antifouling Paints Control Act (June 16 1988) which limits the type of vessel on which these paints can

be used and limits the use of tributyltin paints that have laboratory tested release rates of le4 microgcm2day

(Cardwell et al 1999a) Most industrialized countries in addition to the United States have adopted

similar restrictions on the use of tributyltin containing paints These countries include the United

Kingdom Canada France New Zealand Australia and the European Union (Birchenough et al 2002)

255 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Organotin compounds may also be released to water from overspray and land runoff from agricultural

applications industrial processes and leaching from organotin-stabilized polyvinyl chloride (PVC)

(Blunden et al 1984) The use of tributyltin compounds as slimicides on masonry disinfectants and

biocides for cooling systems power station cooling towers pulp and paper mills breweries leather

processing and textile mills may result in their release to the environment (WHO 1990) Triphenyltin

acetate and triphenyltin hydroxide are used as fungicides algicides and molluscicides (WHO 1999)

Timber treatment facilities can be as a significant source of tributyltin in freshwater systems from

seepage accidental spills and intentional releases Minor sources of organotin compounds in freshwater

can be seepage from landfill sites and agricultural runoff due to the use of contaminated sewage sludge or

organotin containing pesticides (Demora and Pelletier 1997) Monthly samples of influent effluent and

sludges were collected from July 1990 to January 1991 from sewage treatment plants in five Canadian

cities Monobutyltin was detected in all influent samples Dibutyl- and tributyltin were only detected

infrequently and octyltin species were not detected A significant reduction 40 on average in the

concentration of monomethyltin was found after passage through the sewage treatment plants due to

degradation and adsorption to sludge No butyltin or octyltin species were found in five landfill leachate

samples in southern Ontario Canada (Chau et al 1992)

623 Soil

There is no information on releases of tin and tin compounds to soil from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in soil at 121 sites and in sediment at 49 sites collected from 214 NPL hazardous

waste sites where it was detected in some environmental media Organotin compounds were found in

sediment and soil at four sites and one site respectively of the eight current or former NPL hazardous

waste sites where they were detected in some environmental media (HazDat 2004)

Tin may be released to soil from organotin pesticide usage and landfilling of tin-containing wastes

including used cans and organotin-containing plastics (WHO 1980) The application of pre-treated

municipal sludge and urban refuse as soil amendments may also introduce tin to soils Concentrations of

tin in sewage sludges from countries in Europe and North America ranged from 40 to 700 mgkg dry

weight Manures and poultry wastes contained tin at concentrations of 37ndash74 and 20ndash41 mgkg dry

weight respectively Other incidental point sources that may introduce tin to soil are corrosion of metal

objects and dispersion of metallic ores during transport (Senesi et al 1999) Organotin compounds may

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

TIN AND TIN COMPOUNDS 251

6 POTENTIAL FOR HUMAN EXPOSURE

Figure 6-2 Frequency of NPL Sites with Organotin Contamination

Frequency of NPL Sites

1 3

Derived from HazDat 2005

252 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

weathering cycle (Wedepohl et al 1978) Tin in water may partition to soils and sediments Cations such

as Sn2+ and Sn4+ will generally be adsorbed by soils to some extent which reduces their mobility Tin is

generally regarded as being relatively immobile in the environment (Gerritse et al 1982 WHO 1980)

Organotin compounds are generally only sparingly soluble in water and are likely to partition to soils and

sediments Most commercially used organotin compounds are relatively immobile in environmental

media due to their low vapor pressures low water solubilities and high affinities for soil and organic

sediments (Blunden et al 1984) For example nearly all of the tributyltin found in the water column is

bound to suspended particles with a small portion associated with dissolved organic matter and organic

and inorganic ligands (Gadd 2000) Tributyltin that is associated with particles in the water column may

settle out which is an important process in its removal from the water column Tributyltin sorption

coefficients to sediments can range from 100 to 10000 (Anderson et al 2002) Degradation of organotin

compounds involves breaking the tin-carbon bond and can occur in the environment by ultraviolet (UV)

irradiation or biological or chemical cleavage (Blunden et al 1984) Rates of photodegradation and

biodegradation of organotins in water are dependent upon environmental conditions In sediment

organotins are generally persistent Organotin compounds may be significantly bioconcentrated by

aquatic organisms Cleavage of the tin-carbon bond by hydrolysis is not a significant environmental fate

process under environmental conditions (WHO 1990)

Occupational exposure to tin may be significant in some industrial environments Ambient environshy

mental levels of tin are generally quite low except in the vicinity of pollution sources Humans may be

exposed to tin by inhalation ingestion or dermal absorption However typical human exposure to tin is

primarily by ingestion of food Tin-lined cans used to package food constitute the most important

contribution to tin intake in the diet (Bieacutego et al 1999) While there is evidence that tin is essential for

the normal growth of rats there is no evidence that tin is essential for other animals including humans

(WHO 1980) Exposure to organotin compounds may occur by the ingestion of seafood and contact with

consumer products that contain organotin compounds Household commodities made up of polyurethane

plastic polymers and silicons contain butyltin concentrations in the parts per million range (Kannan et al

1999) Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in drinking

water in Canada where polyvinyl chloride (PVC) pipes containing these organotin compounds are used

in the distribution of drinking water (Sadiki and Williams 1996 1999 Sadiki et al 1996) Organotin

compounds were detected in household dust in the United Kingdom (Santillo et al 2003)

253 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

62 RELEASES TO THE ENVIRONMENT

The Toxics Release Inventory (TRI) data should be used with caution because only certain types of

facilities are required to report (EPA 1997) Manufacturing and processing facilities are required to report

information to the TRI only if they employ 10 or more full-time employees if their facility is classified

under Standard Industrial Classification (SIC) codes 20ndash39 and if their facility produces imports or

processes ge25000 pounds of any TRI chemical or otherwise uses gt10000 pounds of a TRI chemical in a

calendar year (EPA 1997)

There is no information on releases of tin and tin compounds from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997) However releases of tin to

environmental media may occur from the production and use of tin and tin compounds

Tin and organotin compounds have been identified in a variety of environmental media (air surface

water leachate groundwater soil and sediment) collected at 214 and 8 sites respectively of the

1662 current or former NPL hazardous waste sites (HazDat 2004)

621 Air

There is no information on releases of tin and tin compounds to the atmosphere from manufacturing and

processing facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in air collected at 6 of the 214 current or former NPL hazardous waste sites where

it was detected in some environmental media No organotin compounds were found in air at the eight

current or former NPL hazardous waste sites where organotin compounds were detected in some

environmental media (HazDat 2004)

Tin may be released to the atmosphere from both natural and anthropogenic sources Tin is a component

of many soils and may be released in dusts from wind storms roads and agricultural activities Gases

dusts and fumes containing tin may be released from smelting and refining processes industrial uses of

tin waste incineration and burning of fossil fuels (Byrd and Andreae 1986 Senesi et al 1999 WHO

1980) Davison et al (1974) reported that the tin content of airborne fly ash from coal-burning power

plants ranged from 7 to 19 microgg Worldwide emissions of tin to the atmosphere from coal and oil

combustion refuse incineration and coppernickel production facilities were estimated at 1470ndash

254 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

10810 metric tons in 1983 (Nriagu and Pacyna 1988) Organotin compounds may be released to air by

agricultural spraying volatilization antifouling paint sprays incineration of materials treated or stabilized

with organotin compounds and glass coating operations Incineration of organotin containing material is

unlikely to be a significant source of organotin compounds to air since these compounds will be

decomposed to inorganic tin during combustion (Blunden et al 1984) Releases of organotin compounds

to air are not significant due to their low vapor pressures and rapid photodegradation (Blunden et al 1984

Fent 1996)

622 Water

There is no information on releases of tin and tin compounds to water from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in groundwater and surface water at 78 and 36 sites respectively of the 214 NPL

hazardous waste sites where it was detected in some environmental media Organotin compounds were

found in surface water at one of the eight current or former NPL hazardous waste sites where they were

detected in some environmental media organotin compounds were not found in groundwater at these

sites (HazDat 2004)

Releases of tin to water may occur from industrial facilities smelting refining or using tin (WHO 1980)

Antifouling paints containing tributyltin are applied as a finish coat to the immersed sections of boats and

floating structures As the paint releases tributyltin into the water it creates an environment that repels

the organisms that may attach to the surface of submerged objects Use of antifouling paints represents

the major source of tributyltin into the coastal environment It has been estimated that one boat releases

1ndash10 microg tributyltincm2 of hull surface daily to ensure antifouling protection This corresponds to 02ndash

2 gday for a small sailboat and up to 50ndash500 gday for an average sized merchant ship (Alzieu 1998)

The use of triorganotin compounds as marine antifoulants has been restricted by the Organotin

Antifouling Paints Control Act (June 16 1988) which limits the type of vessel on which these paints can

be used and limits the use of tributyltin paints that have laboratory tested release rates of le4 microgcm2day

(Cardwell et al 1999a) Most industrialized countries in addition to the United States have adopted

similar restrictions on the use of tributyltin containing paints These countries include the United

Kingdom Canada France New Zealand Australia and the European Union (Birchenough et al 2002)

255 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Organotin compounds may also be released to water from overspray and land runoff from agricultural

applications industrial processes and leaching from organotin-stabilized polyvinyl chloride (PVC)

(Blunden et al 1984) The use of tributyltin compounds as slimicides on masonry disinfectants and

biocides for cooling systems power station cooling towers pulp and paper mills breweries leather

processing and textile mills may result in their release to the environment (WHO 1990) Triphenyltin

acetate and triphenyltin hydroxide are used as fungicides algicides and molluscicides (WHO 1999)

Timber treatment facilities can be as a significant source of tributyltin in freshwater systems from

seepage accidental spills and intentional releases Minor sources of organotin compounds in freshwater

can be seepage from landfill sites and agricultural runoff due to the use of contaminated sewage sludge or

organotin containing pesticides (Demora and Pelletier 1997) Monthly samples of influent effluent and

sludges were collected from July 1990 to January 1991 from sewage treatment plants in five Canadian

cities Monobutyltin was detected in all influent samples Dibutyl- and tributyltin were only detected

infrequently and octyltin species were not detected A significant reduction 40 on average in the

concentration of monomethyltin was found after passage through the sewage treatment plants due to

degradation and adsorption to sludge No butyltin or octyltin species were found in five landfill leachate

samples in southern Ontario Canada (Chau et al 1992)

623 Soil

There is no information on releases of tin and tin compounds to soil from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in soil at 121 sites and in sediment at 49 sites collected from 214 NPL hazardous

waste sites where it was detected in some environmental media Organotin compounds were found in

sediment and soil at four sites and one site respectively of the eight current or former NPL hazardous

waste sites where they were detected in some environmental media (HazDat 2004)

Tin may be released to soil from organotin pesticide usage and landfilling of tin-containing wastes

including used cans and organotin-containing plastics (WHO 1980) The application of pre-treated

municipal sludge and urban refuse as soil amendments may also introduce tin to soils Concentrations of

tin in sewage sludges from countries in Europe and North America ranged from 40 to 700 mgkg dry

weight Manures and poultry wastes contained tin at concentrations of 37ndash74 and 20ndash41 mgkg dry

weight respectively Other incidental point sources that may introduce tin to soil are corrosion of metal

objects and dispersion of metallic ores during transport (Senesi et al 1999) Organotin compounds may

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

252 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

weathering cycle (Wedepohl et al 1978) Tin in water may partition to soils and sediments Cations such

as Sn2+ and Sn4+ will generally be adsorbed by soils to some extent which reduces their mobility Tin is

generally regarded as being relatively immobile in the environment (Gerritse et al 1982 WHO 1980)

Organotin compounds are generally only sparingly soluble in water and are likely to partition to soils and

sediments Most commercially used organotin compounds are relatively immobile in environmental

media due to their low vapor pressures low water solubilities and high affinities for soil and organic

sediments (Blunden et al 1984) For example nearly all of the tributyltin found in the water column is

bound to suspended particles with a small portion associated with dissolved organic matter and organic

and inorganic ligands (Gadd 2000) Tributyltin that is associated with particles in the water column may

settle out which is an important process in its removal from the water column Tributyltin sorption

coefficients to sediments can range from 100 to 10000 (Anderson et al 2002) Degradation of organotin

compounds involves breaking the tin-carbon bond and can occur in the environment by ultraviolet (UV)

irradiation or biological or chemical cleavage (Blunden et al 1984) Rates of photodegradation and

biodegradation of organotins in water are dependent upon environmental conditions In sediment

organotins are generally persistent Organotin compounds may be significantly bioconcentrated by

aquatic organisms Cleavage of the tin-carbon bond by hydrolysis is not a significant environmental fate

process under environmental conditions (WHO 1990)

Occupational exposure to tin may be significant in some industrial environments Ambient environshy

mental levels of tin are generally quite low except in the vicinity of pollution sources Humans may be

exposed to tin by inhalation ingestion or dermal absorption However typical human exposure to tin is

primarily by ingestion of food Tin-lined cans used to package food constitute the most important

contribution to tin intake in the diet (Bieacutego et al 1999) While there is evidence that tin is essential for

the normal growth of rats there is no evidence that tin is essential for other animals including humans

(WHO 1980) Exposure to organotin compounds may occur by the ingestion of seafood and contact with

consumer products that contain organotin compounds Household commodities made up of polyurethane

plastic polymers and silicons contain butyltin concentrations in the parts per million range (Kannan et al

1999) Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in drinking

water in Canada where polyvinyl chloride (PVC) pipes containing these organotin compounds are used

in the distribution of drinking water (Sadiki and Williams 1996 1999 Sadiki et al 1996) Organotin

compounds were detected in household dust in the United Kingdom (Santillo et al 2003)

253 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

62 RELEASES TO THE ENVIRONMENT

The Toxics Release Inventory (TRI) data should be used with caution because only certain types of

facilities are required to report (EPA 1997) Manufacturing and processing facilities are required to report

information to the TRI only if they employ 10 or more full-time employees if their facility is classified

under Standard Industrial Classification (SIC) codes 20ndash39 and if their facility produces imports or

processes ge25000 pounds of any TRI chemical or otherwise uses gt10000 pounds of a TRI chemical in a

calendar year (EPA 1997)

There is no information on releases of tin and tin compounds from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997) However releases of tin to

environmental media may occur from the production and use of tin and tin compounds

Tin and organotin compounds have been identified in a variety of environmental media (air surface

water leachate groundwater soil and sediment) collected at 214 and 8 sites respectively of the

1662 current or former NPL hazardous waste sites (HazDat 2004)

621 Air

There is no information on releases of tin and tin compounds to the atmosphere from manufacturing and

processing facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in air collected at 6 of the 214 current or former NPL hazardous waste sites where

it was detected in some environmental media No organotin compounds were found in air at the eight

current or former NPL hazardous waste sites where organotin compounds were detected in some

environmental media (HazDat 2004)

Tin may be released to the atmosphere from both natural and anthropogenic sources Tin is a component

of many soils and may be released in dusts from wind storms roads and agricultural activities Gases

dusts and fumes containing tin may be released from smelting and refining processes industrial uses of

tin waste incineration and burning of fossil fuels (Byrd and Andreae 1986 Senesi et al 1999 WHO

1980) Davison et al (1974) reported that the tin content of airborne fly ash from coal-burning power

plants ranged from 7 to 19 microgg Worldwide emissions of tin to the atmosphere from coal and oil

combustion refuse incineration and coppernickel production facilities were estimated at 1470ndash

254 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

10810 metric tons in 1983 (Nriagu and Pacyna 1988) Organotin compounds may be released to air by

agricultural spraying volatilization antifouling paint sprays incineration of materials treated or stabilized

with organotin compounds and glass coating operations Incineration of organotin containing material is

unlikely to be a significant source of organotin compounds to air since these compounds will be

decomposed to inorganic tin during combustion (Blunden et al 1984) Releases of organotin compounds

to air are not significant due to their low vapor pressures and rapid photodegradation (Blunden et al 1984

Fent 1996)

622 Water

There is no information on releases of tin and tin compounds to water from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in groundwater and surface water at 78 and 36 sites respectively of the 214 NPL

hazardous waste sites where it was detected in some environmental media Organotin compounds were

found in surface water at one of the eight current or former NPL hazardous waste sites where they were

detected in some environmental media organotin compounds were not found in groundwater at these

sites (HazDat 2004)

Releases of tin to water may occur from industrial facilities smelting refining or using tin (WHO 1980)

Antifouling paints containing tributyltin are applied as a finish coat to the immersed sections of boats and

floating structures As the paint releases tributyltin into the water it creates an environment that repels

the organisms that may attach to the surface of submerged objects Use of antifouling paints represents

the major source of tributyltin into the coastal environment It has been estimated that one boat releases

1ndash10 microg tributyltincm2 of hull surface daily to ensure antifouling protection This corresponds to 02ndash

2 gday for a small sailboat and up to 50ndash500 gday for an average sized merchant ship (Alzieu 1998)

The use of triorganotin compounds as marine antifoulants has been restricted by the Organotin

Antifouling Paints Control Act (June 16 1988) which limits the type of vessel on which these paints can

be used and limits the use of tributyltin paints that have laboratory tested release rates of le4 microgcm2day

(Cardwell et al 1999a) Most industrialized countries in addition to the United States have adopted

similar restrictions on the use of tributyltin containing paints These countries include the United

Kingdom Canada France New Zealand Australia and the European Union (Birchenough et al 2002)

255 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Organotin compounds may also be released to water from overspray and land runoff from agricultural

applications industrial processes and leaching from organotin-stabilized polyvinyl chloride (PVC)

(Blunden et al 1984) The use of tributyltin compounds as slimicides on masonry disinfectants and

biocides for cooling systems power station cooling towers pulp and paper mills breweries leather

processing and textile mills may result in their release to the environment (WHO 1990) Triphenyltin

acetate and triphenyltin hydroxide are used as fungicides algicides and molluscicides (WHO 1999)

Timber treatment facilities can be as a significant source of tributyltin in freshwater systems from

seepage accidental spills and intentional releases Minor sources of organotin compounds in freshwater

can be seepage from landfill sites and agricultural runoff due to the use of contaminated sewage sludge or

organotin containing pesticides (Demora and Pelletier 1997) Monthly samples of influent effluent and

sludges were collected from July 1990 to January 1991 from sewage treatment plants in five Canadian

cities Monobutyltin was detected in all influent samples Dibutyl- and tributyltin were only detected

infrequently and octyltin species were not detected A significant reduction 40 on average in the

concentration of monomethyltin was found after passage through the sewage treatment plants due to

degradation and adsorption to sludge No butyltin or octyltin species were found in five landfill leachate

samples in southern Ontario Canada (Chau et al 1992)

623 Soil

There is no information on releases of tin and tin compounds to soil from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in soil at 121 sites and in sediment at 49 sites collected from 214 NPL hazardous

waste sites where it was detected in some environmental media Organotin compounds were found in

sediment and soil at four sites and one site respectively of the eight current or former NPL hazardous

waste sites where they were detected in some environmental media (HazDat 2004)

Tin may be released to soil from organotin pesticide usage and landfilling of tin-containing wastes

including used cans and organotin-containing plastics (WHO 1980) The application of pre-treated

municipal sludge and urban refuse as soil amendments may also introduce tin to soils Concentrations of

tin in sewage sludges from countries in Europe and North America ranged from 40 to 700 mgkg dry

weight Manures and poultry wastes contained tin at concentrations of 37ndash74 and 20ndash41 mgkg dry

weight respectively Other incidental point sources that may introduce tin to soil are corrosion of metal

objects and dispersion of metallic ores during transport (Senesi et al 1999) Organotin compounds may

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

253 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

62 RELEASES TO THE ENVIRONMENT

The Toxics Release Inventory (TRI) data should be used with caution because only certain types of

facilities are required to report (EPA 1997) Manufacturing and processing facilities are required to report

information to the TRI only if they employ 10 or more full-time employees if their facility is classified

under Standard Industrial Classification (SIC) codes 20ndash39 and if their facility produces imports or

processes ge25000 pounds of any TRI chemical or otherwise uses gt10000 pounds of a TRI chemical in a

calendar year (EPA 1997)

There is no information on releases of tin and tin compounds from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997) However releases of tin to

environmental media may occur from the production and use of tin and tin compounds

Tin and organotin compounds have been identified in a variety of environmental media (air surface

water leachate groundwater soil and sediment) collected at 214 and 8 sites respectively of the

1662 current or former NPL hazardous waste sites (HazDat 2004)

621 Air

There is no information on releases of tin and tin compounds to the atmosphere from manufacturing and

processing facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in air collected at 6 of the 214 current or former NPL hazardous waste sites where

it was detected in some environmental media No organotin compounds were found in air at the eight

current or former NPL hazardous waste sites where organotin compounds were detected in some

environmental media (HazDat 2004)

Tin may be released to the atmosphere from both natural and anthropogenic sources Tin is a component

of many soils and may be released in dusts from wind storms roads and agricultural activities Gases

dusts and fumes containing tin may be released from smelting and refining processes industrial uses of

tin waste incineration and burning of fossil fuels (Byrd and Andreae 1986 Senesi et al 1999 WHO

1980) Davison et al (1974) reported that the tin content of airborne fly ash from coal-burning power

plants ranged from 7 to 19 microgg Worldwide emissions of tin to the atmosphere from coal and oil

combustion refuse incineration and coppernickel production facilities were estimated at 1470ndash

254 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

10810 metric tons in 1983 (Nriagu and Pacyna 1988) Organotin compounds may be released to air by

agricultural spraying volatilization antifouling paint sprays incineration of materials treated or stabilized

with organotin compounds and glass coating operations Incineration of organotin containing material is

unlikely to be a significant source of organotin compounds to air since these compounds will be

decomposed to inorganic tin during combustion (Blunden et al 1984) Releases of organotin compounds

to air are not significant due to their low vapor pressures and rapid photodegradation (Blunden et al 1984

Fent 1996)

622 Water

There is no information on releases of tin and tin compounds to water from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in groundwater and surface water at 78 and 36 sites respectively of the 214 NPL

hazardous waste sites where it was detected in some environmental media Organotin compounds were

found in surface water at one of the eight current or former NPL hazardous waste sites where they were

detected in some environmental media organotin compounds were not found in groundwater at these

sites (HazDat 2004)

Releases of tin to water may occur from industrial facilities smelting refining or using tin (WHO 1980)

Antifouling paints containing tributyltin are applied as a finish coat to the immersed sections of boats and

floating structures As the paint releases tributyltin into the water it creates an environment that repels

the organisms that may attach to the surface of submerged objects Use of antifouling paints represents

the major source of tributyltin into the coastal environment It has been estimated that one boat releases

1ndash10 microg tributyltincm2 of hull surface daily to ensure antifouling protection This corresponds to 02ndash

2 gday for a small sailboat and up to 50ndash500 gday for an average sized merchant ship (Alzieu 1998)

The use of triorganotin compounds as marine antifoulants has been restricted by the Organotin

Antifouling Paints Control Act (June 16 1988) which limits the type of vessel on which these paints can

be used and limits the use of tributyltin paints that have laboratory tested release rates of le4 microgcm2day

(Cardwell et al 1999a) Most industrialized countries in addition to the United States have adopted

similar restrictions on the use of tributyltin containing paints These countries include the United

Kingdom Canada France New Zealand Australia and the European Union (Birchenough et al 2002)

255 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Organotin compounds may also be released to water from overspray and land runoff from agricultural

applications industrial processes and leaching from organotin-stabilized polyvinyl chloride (PVC)

(Blunden et al 1984) The use of tributyltin compounds as slimicides on masonry disinfectants and

biocides for cooling systems power station cooling towers pulp and paper mills breweries leather

processing and textile mills may result in their release to the environment (WHO 1990) Triphenyltin

acetate and triphenyltin hydroxide are used as fungicides algicides and molluscicides (WHO 1999)

Timber treatment facilities can be as a significant source of tributyltin in freshwater systems from

seepage accidental spills and intentional releases Minor sources of organotin compounds in freshwater

can be seepage from landfill sites and agricultural runoff due to the use of contaminated sewage sludge or

organotin containing pesticides (Demora and Pelletier 1997) Monthly samples of influent effluent and

sludges were collected from July 1990 to January 1991 from sewage treatment plants in five Canadian

cities Monobutyltin was detected in all influent samples Dibutyl- and tributyltin were only detected

infrequently and octyltin species were not detected A significant reduction 40 on average in the

concentration of monomethyltin was found after passage through the sewage treatment plants due to

degradation and adsorption to sludge No butyltin or octyltin species were found in five landfill leachate

samples in southern Ontario Canada (Chau et al 1992)

623 Soil

There is no information on releases of tin and tin compounds to soil from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in soil at 121 sites and in sediment at 49 sites collected from 214 NPL hazardous

waste sites where it was detected in some environmental media Organotin compounds were found in

sediment and soil at four sites and one site respectively of the eight current or former NPL hazardous

waste sites where they were detected in some environmental media (HazDat 2004)

Tin may be released to soil from organotin pesticide usage and landfilling of tin-containing wastes

including used cans and organotin-containing plastics (WHO 1980) The application of pre-treated

municipal sludge and urban refuse as soil amendments may also introduce tin to soils Concentrations of

tin in sewage sludges from countries in Europe and North America ranged from 40 to 700 mgkg dry

weight Manures and poultry wastes contained tin at concentrations of 37ndash74 and 20ndash41 mgkg dry

weight respectively Other incidental point sources that may introduce tin to soil are corrosion of metal

objects and dispersion of metallic ores during transport (Senesi et al 1999) Organotin compounds may

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

254 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

10810 metric tons in 1983 (Nriagu and Pacyna 1988) Organotin compounds may be released to air by

agricultural spraying volatilization antifouling paint sprays incineration of materials treated or stabilized

with organotin compounds and glass coating operations Incineration of organotin containing material is

unlikely to be a significant source of organotin compounds to air since these compounds will be

decomposed to inorganic tin during combustion (Blunden et al 1984) Releases of organotin compounds

to air are not significant due to their low vapor pressures and rapid photodegradation (Blunden et al 1984

Fent 1996)

622 Water

There is no information on releases of tin and tin compounds to water from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in groundwater and surface water at 78 and 36 sites respectively of the 214 NPL

hazardous waste sites where it was detected in some environmental media Organotin compounds were

found in surface water at one of the eight current or former NPL hazardous waste sites where they were

detected in some environmental media organotin compounds were not found in groundwater at these

sites (HazDat 2004)

Releases of tin to water may occur from industrial facilities smelting refining or using tin (WHO 1980)

Antifouling paints containing tributyltin are applied as a finish coat to the immersed sections of boats and

floating structures As the paint releases tributyltin into the water it creates an environment that repels

the organisms that may attach to the surface of submerged objects Use of antifouling paints represents

the major source of tributyltin into the coastal environment It has been estimated that one boat releases

1ndash10 microg tributyltincm2 of hull surface daily to ensure antifouling protection This corresponds to 02ndash

2 gday for a small sailboat and up to 50ndash500 gday for an average sized merchant ship (Alzieu 1998)

The use of triorganotin compounds as marine antifoulants has been restricted by the Organotin

Antifouling Paints Control Act (June 16 1988) which limits the type of vessel on which these paints can

be used and limits the use of tributyltin paints that have laboratory tested release rates of le4 microgcm2day

(Cardwell et al 1999a) Most industrialized countries in addition to the United States have adopted

similar restrictions on the use of tributyltin containing paints These countries include the United

Kingdom Canada France New Zealand Australia and the European Union (Birchenough et al 2002)

255 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Organotin compounds may also be released to water from overspray and land runoff from agricultural

applications industrial processes and leaching from organotin-stabilized polyvinyl chloride (PVC)

(Blunden et al 1984) The use of tributyltin compounds as slimicides on masonry disinfectants and

biocides for cooling systems power station cooling towers pulp and paper mills breweries leather

processing and textile mills may result in their release to the environment (WHO 1990) Triphenyltin

acetate and triphenyltin hydroxide are used as fungicides algicides and molluscicides (WHO 1999)

Timber treatment facilities can be as a significant source of tributyltin in freshwater systems from

seepage accidental spills and intentional releases Minor sources of organotin compounds in freshwater

can be seepage from landfill sites and agricultural runoff due to the use of contaminated sewage sludge or

organotin containing pesticides (Demora and Pelletier 1997) Monthly samples of influent effluent and

sludges were collected from July 1990 to January 1991 from sewage treatment plants in five Canadian

cities Monobutyltin was detected in all influent samples Dibutyl- and tributyltin were only detected

infrequently and octyltin species were not detected A significant reduction 40 on average in the

concentration of monomethyltin was found after passage through the sewage treatment plants due to

degradation and adsorption to sludge No butyltin or octyltin species were found in five landfill leachate

samples in southern Ontario Canada (Chau et al 1992)

623 Soil

There is no information on releases of tin and tin compounds to soil from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in soil at 121 sites and in sediment at 49 sites collected from 214 NPL hazardous

waste sites where it was detected in some environmental media Organotin compounds were found in

sediment and soil at four sites and one site respectively of the eight current or former NPL hazardous

waste sites where they were detected in some environmental media (HazDat 2004)

Tin may be released to soil from organotin pesticide usage and landfilling of tin-containing wastes

including used cans and organotin-containing plastics (WHO 1980) The application of pre-treated

municipal sludge and urban refuse as soil amendments may also introduce tin to soils Concentrations of

tin in sewage sludges from countries in Europe and North America ranged from 40 to 700 mgkg dry

weight Manures and poultry wastes contained tin at concentrations of 37ndash74 and 20ndash41 mgkg dry

weight respectively Other incidental point sources that may introduce tin to soil are corrosion of metal

objects and dispersion of metallic ores during transport (Senesi et al 1999) Organotin compounds may

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

255 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Organotin compounds may also be released to water from overspray and land runoff from agricultural

applications industrial processes and leaching from organotin-stabilized polyvinyl chloride (PVC)

(Blunden et al 1984) The use of tributyltin compounds as slimicides on masonry disinfectants and

biocides for cooling systems power station cooling towers pulp and paper mills breweries leather

processing and textile mills may result in their release to the environment (WHO 1990) Triphenyltin

acetate and triphenyltin hydroxide are used as fungicides algicides and molluscicides (WHO 1999)

Timber treatment facilities can be as a significant source of tributyltin in freshwater systems from

seepage accidental spills and intentional releases Minor sources of organotin compounds in freshwater

can be seepage from landfill sites and agricultural runoff due to the use of contaminated sewage sludge or

organotin containing pesticides (Demora and Pelletier 1997) Monthly samples of influent effluent and

sludges were collected from July 1990 to January 1991 from sewage treatment plants in five Canadian

cities Monobutyltin was detected in all influent samples Dibutyl- and tributyltin were only detected

infrequently and octyltin species were not detected A significant reduction 40 on average in the

concentration of monomethyltin was found after passage through the sewage treatment plants due to

degradation and adsorption to sludge No butyltin or octyltin species were found in five landfill leachate

samples in southern Ontario Canada (Chau et al 1992)

623 Soil

There is no information on releases of tin and tin compounds to soil from manufacturing and processing

facilities because these releases are not required to be reported (EPA 1997)

Tin has been identified in soil at 121 sites and in sediment at 49 sites collected from 214 NPL hazardous

waste sites where it was detected in some environmental media Organotin compounds were found in

sediment and soil at four sites and one site respectively of the eight current or former NPL hazardous

waste sites where they were detected in some environmental media (HazDat 2004)

Tin may be released to soil from organotin pesticide usage and landfilling of tin-containing wastes

including used cans and organotin-containing plastics (WHO 1980) The application of pre-treated

municipal sludge and urban refuse as soil amendments may also introduce tin to soils Concentrations of

tin in sewage sludges from countries in Europe and North America ranged from 40 to 700 mgkg dry

weight Manures and poultry wastes contained tin at concentrations of 37ndash74 and 20ndash41 mgkg dry

weight respectively Other incidental point sources that may introduce tin to soil are corrosion of metal

objects and dispersion of metallic ores during transport (Senesi et al 1999) Organotin compounds may

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

256 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

be released to soil through agricultural applications and burial of organotin-containing waste material

(Blunden et al 1984) An estimated 5200 tons of organotin compounds were released primarily to

landfills in the United States in 1976 (Laughlin and Linden 1985) No current data were found regarding

releases of organotin compounds to soil

63 ENVIRONMENTAL FATE

631 Transport and Partitioning

Tin may be transported in the atmosphere by the release of particulate matter derived from the

combustion of fossil fuels and solid wastes The vapor pressure of elemental tin is negligible (Cooper and

Stranks 1966) and inorganic tin compounds are nonvolatile at environmental conditions Airborne

particles may travel long distances before deposition depending on the type of emitting source physical

form and properties (eg size density) physical or chemical changes that may occur during transport

adsorption processes and meteorological conditions (Senesi et al 1999)

Tin may exist in either divalent (Sn2+) or tetravalent (Sn4+) cationic (positively charged) ions at

environmental conditions Tin(II) dominates in reduced (oxygen-poor) water and will readily precipitate

as a sulfide (SnS) or as a hydroxide (Sn(OH)2) in alkaline water Tin(IV) readily hydrolyzes and can

precipitate as a hydroxide The solubility product of Sn(OH)4 has been measured at approximately

10-56 gL at 25 degC In general tin(IV) would be expected to be the only stable ionic species in the

weathering cycle (Wedepohl et al 1978)

Tin in water may partition to soils and sediments Cations such as Sn2+ and Sn4+ will generally be

adsorbed by soils to some extent which reduces their mobility Tin is generally regarded as being

relatively immobile in the environment (Gerritse et al 1982 WHO 1980) However tin may be

transported in water if it partitions to suspended sediments (Cooney 1988) but the significance of this

mechanism has not been studied in detail Transfer coefficients for tin in a soil-plant system were

reported to be 001ndash01 (Senesi et al 1999)

A bioconcentration factor (BCF) relates the concentration of a chemical in plants and animals to the

concentration of the chemical in the medium in which they live It was estimated that the BCFs of

inorganic tin were 100 1000 and 3000 for marine and freshwater plants invertebrates and fish

respectively (Thompson et al 1972) Marine algae can bioconcentrate tin(IV) ion by a factor of

1900 (Seidel et al 1980)

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

257 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Approximately 95 of tributyltin in the water column was found to be bound to suspended particles and

the remainder was associated with dissolved organic matter and organic and inorganic ligands (Gadd

2000) Tributyltin that is associated with particles in the water column may settle out which is an

important process in the removal of tributyltin from the water column Tributyltin sorption coefficients to

sediments can range from 100 to 10000 (Anderson et al 2002) A partition coefficient of about 2180 at

20 degC was calculated by Maguire et al (1985) to estimate the adsorption of tributyltin ions by lake

sediments These investigations also concluded that the half-life of the desorption reaction was about

10 months indicating that tributyltin can be strongly retained by sediments The adsorption behavior of

Sn4+ ion and eight organotin species (tri- di- and monobutyltin tri- di- and monomethyltin and tri- and

diphenyltin) were studied in a water-sediment system using artificial seawater and estuarine sediment

Adsorption coefficients varied from 1005 to 1045 and showed the trend of Sn4+ gt mono gt di gt tri in the

same substituent series Larger absorption coefficients were found for aromatic compounds than for

aliphatic compounds (Sun et al 1996) Sediment-water partition coefficients for tributyltin ranged from

240 to 65000 in sediments of the coast of southwestern Spain Similar values were found for

monobutyltin Dibutyltin was found to have higher affinity for sediment (Gomez-Ariza et al 2001)

At ambient temperatures the solubilities of organotin compounds range from 00001 to about 50 mgL

(Laughlin and Linden 1985 WHO 1980) Organotin compounds may partition from water to aquatic

organisms An octanolwater partition coefficient (Kow) describes the partitioning of an organic chemical

between octanol and water Octanol is believed to best imitate the fatty structures in plant and animal

tissues (Kenaga and Goring 1980) The Kow of tributyltin at pH 6 was reported to be about 1585 by

Maguire et al (1983) The most accurate Kow for tributyltin in seawater was 5500 (Laughlin and Linden

1985)

There is no evidence of biomagnification of tributyltin in marine ecosystems but accumulation may

occur resulting in high tissue concentrations in some organisms (Meador 2000) Ruumldel (2003) reported

that based on a review of the literature the bioavailability of organotin compounds via the food chain

appears to be of minor importance for tributyltin and triphenyltin when compared to uptake via the water

phase Measured BCF values for bis(tributyltin)oxide with marine oysters were found to range from

2300 to 11400 (Waldock and Thain 1983) A BCF of 30000 was estimated by Maguire et al (1984) for

the bioconcentration of tributyltin cation by freshwater green algae Seven-day BCF values were derived

for dibutyltin dichloride dibutyltin dilaurate tributyltin chloride bis(tributyltin) oxide and triphenyltin

chloride for muscle liver kidney and vertebra tissue of round crucian carp The BCF values ranged

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

258 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 12 in muscle to 5012 in liver For all organotin compounds liver had the highest BCF values The

highest BCFs were found for the tributyltin compounds (Tsuda et al 1986) BCF values for

bis(tributyltin) oxide for red sea bream (Pagrus major) mullet (Mugil cephalus) and filefish (Rudarius

erodes) were 9400ndash11000 2400ndash3000 and 3200ndash3600 respectively determined in an 8-week flow-

through aquarium system Larger BCF values were obtained when fish were reared in seawater

containing lower concentrations of tributyltin BCF values for triphenyltin chloride for P major and

R erodes were 3100ndash3300 and 4100 respectively and were independent of the concentration of

triphenyltin in the rearing water (Yamada and Takayanagi 1992) The log BCFs for tributyltin in fish

from the Port of Osaka and the Yodo River Japan were 36ndash42 and 29ndash35 respectively (Harino et al

2000) After 50 days of exposure to water containing a constant concentration of tributyltin (500 ngL)

whole body concentrations in tilapia did not reach a plateau and the 50-day BCF was 12300

Enrichment of tributyltin was highest in the viscera followed by gill and then muscle (Hongxia et al

1998) A BCF of 10500 was found for tributyltin uptake from seawater in marine mussels (Mugil

graynus) during the 56-day accumulation phase (Suzuki et al 1998) BCFs were 17000ndash350000 2000ndash

70000 and 1000ndash70000 for tri- di- and monobutylin respectively in mollusks living in southwest

Spain showing a decrease in BCF with decreasing lipophilicity for the butyltin compounds (Gomez-

Ariza et al 2001)

Bioconcentration as a function of pH was studied for triphenyltin and tributyltin in a freshwater sediment

organism Chironomus ripaius At pH 5 and 8 respectively the BCFs were 310 and 170 for tributyltin

and 680 and 510 for triphenyltin While the difference in BCF at the two pHs was statistically significant

for tributyltin it was not for triphenyltin This may be explained by the speciation differences for each of

these compounds as pH varies The acid dissociation constant (pKa) of tributyltin is 625 and at pH 5 the

fraction of tributyltin hydroxide is approximately 5 with the tributyltin cation as the predominant

species in solution The pKa for triphenyltin is 52 and at pH 5 approximately 40 is present as

triphenyltin hydroxide with the remainder as triphenyltin cation The differences in the observed pH

dependence between triphenyltin and tributyltin may indicate that the neutral hydroxide species is the

predominant form taken up by the organism BCF values of 1500 and 1200 at pH 5 and 8 respectively

were determined for tetrabutyltin ion which cannot undergo ionization and was used as a control

compound The difference between these BCF values for tetrabutyltin at pH 5 and 8 was not statistically

significant (Looser et al 1998)

Releases of organotin compounds to air from various surfaces are in general not significant due to their

low vapor pressures and rapid photodegradation at surfaces (Fent 1996) It has been reported that

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

259 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

methylation of inorganic and organotin compounds such as di- and tributyltin are likely to occur in

sediments producing potentially volatile organotin compounds This process may lead to mobilization of

tin species into the water column and possibly into the atmosphere However there is currently no

significant evidence of losses of organotin compounds to the atmosphere (Amouroux et al 2000) There

was no indication that tributyltin in water partitioned to the air during a 62-day period whereas 20 of

the water evaporated (Maguire et al 1983)

632 Transformation and Degradation

6321 Air

No information was located on the transformation or degradation of tin compounds in the atmosphere

6322 Water

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) It has been established that inorganic tin can be

transformed into organometallic forms by microbial methylation (Hallas et al 1982) Inorganic tin may

also be converted to stannane (H4Sn) in extremely anaerobic (oxygen-poor) conditions by macroalgae

(Donard and Weber 1988)

The speciation of organotin compounds is pH-dependent At lower pHs the cationic form will be the

primary form and as the pH is increased the neutral hydroxide compounds will be the predominant

species In the environmentally relevant pH range (pH 5ndash9) the predominant organotin species will be

the neutral hydroxide compounds (ie R3SnOH R2Sn(OH)2 and RSn(OH)3) High concentrations of

chloride favor the formation of chloro species The pKa values for trimethyltin triethyltin tributyltin and

triphenyltin cations are approximately 660 681 625 and 52 respectively (Blunden et al 1984 Fent

1996 Meador 2000)

Degradation of organotin compounds involves the breaking of the tin-carbon bond which may occur by

UV irradiation or by biological or chemical cleavage (Blunden et al 1984) In water tributyltin can be

degraded by photochemical and biological processes relatively rapidly however adsorption onto

suspended particulate material in water followed by sedimentation is a key removal process (De Mora and

Pelletier 1997) The half-life of tributyltin in seawater varies depending on pH temperature turbidity

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

260 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

and light it is generally estimated to be in the range of 1 day to a few weeks (Alzieu 1998)

Biodegradation is the major process in seawaters rich in suspended solids but photolysis in surface

waters exceeds biodegradation in clean seawater Calculated half-lives range from 6 days in summershy

time waters rich in suspended particles to 127 days in clean winter waters (Watanabe et al 1992)

Tributyltin can be degraded by microbial microalgal and fungal populations as well as by some higher

organisms such as fish (Anderson et al 2002) Cleavage of the tin-carbon bond by hydrolysis is not an

important fate process under environmental conditions (WHO 1990)

6323 Sediment and Soil

Inorganic tin cannot be degraded in the environment but may undergo oxidation-reduction ligand

exchange and precipitation reactions (HSDB 2003) Degradation of organotin compounds in sediments

is much slower than in water and half-lives have been estimated to be several years (Alzieu 1998) In

addition to dealkylation of organotin compounds methylation of tin and organotin compounds by

chemical andor biological means may occur The contribution of methylation by biotic and abiotic

mechanisms is not clear This pathway may result in fully substituted and volatile tin compounds

Methylated butyltin compounds such as tributylmethyltin and dibutyldimethyltin have been found in

contaminated harbor sediments and in surface waters (Amouroux et al 2000 Cooney 1988) Methylation

of tin in sediments was found to be positively correlated with increasing organic content in sediment and

to follow predominately a biotic pathway (Hadjispyrou et al 1998)

64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to tin and tin compounds depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens

Concentrations of tin and tin compounds in unpolluted atmospheres and in pristine surface waters are

often so low as to be near the limits of current analytical methods In reviewing data on tin and tin

compounds levels monitored or estimated in the environment it should also be noted that the amount of

chemical identified analytically is not necessarily equivalent to the amount that is bioavailable The

analytical methods available for monitoring tin and tin compounds in a variety of environmental media

are detailed in Chapter 7

Environmental monitoring studies may report concentrations of organotin compounds in various

environmental media in two formats either as mass of tin per unit mass or volume of media or as mass of

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

261 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

organotin ion per unit mass or volume of media To convert mass on a tin basis to mass on an organotin

cation basis multiply by the ratio of the formula weight of the organotin cation to the atomic weight of

tin Conversions are provided in Table 6-1 for various organotin cations For example a tributyltin

(TBT) concentration in sediment reported as 122 ng TBTg would correspond to 50 ng Sng since

tributyltin ion has a mass that is 244 times greater than that of tin

641 Air

Tin is detected in air infrequently and at low concentrations except in the vicinity of industrial sources

Air concentrations in US cities ranged from below the detection limit to 08 microgm3 in several studies

Average concentrations are generally lt01 microgm3 with higher concentrations near some industrial

facilities (EPA 1982a WHO 1980) In some studies tin was not detected in 40ndashgt50 of samples

Atmospheric tin is associated with particulate matter and peak concentrations were found on smaller

respirable particles (1ndash3 microm) (WHO 1980) Samples of airborne inhalable particulate matter were

collected in two urbanindustrial areas in Illinois southeast Chicago and East St Louis over a 2-year

period Average tin concentrations in the fine (lt25 microm) and coarse (25ndash10 microm) particulate fractions

were lt0007 and 0012 microg m3 for East St Louis respectively and lt0007 microg m3 for both the fine and

course fractions in samples from southeast Chicago and a rural site in Bondville Illinois (Sweet and

Vermette 1993) The average tin concentration in highway tunnel exhaust aerosol in the Elbtunnel in

Hamburg Germany between August 1988 and January 1989 was 109 microgm3 (Dannecker et al 1990)

Tin concentrations in the particulate matter in the ambient air at art glass manufacturing plants measured

by personal samples from oven-charger and batch-mixer workers ranged from 01 to 35 microgm3 from three

plants that use arsenic as a fining agent (a fining agent is added to disperse air bubbles in glass) Tin was

not detected in the particulate matter in the air at three other plants that use antimony compounds instead

of arsenic (Apostoli et al 1998) No monitoring data for concentrations of organotin compounds in air

were found

642 Water

Tin occurs in trace amounts in natural waters However it is seldom measured and only infrequently

detected since concentrations are often below the detection limit (NAS 1977 WHO 1980) In surface

waters tin was detected in only 3 of 59 samples from 15 US and Canadian rivers at concentrations

ranging from 13 to 21 microgL and not detected in 119 samples from 28 US rivers A mean tin

concentration of 0038 microgL was reported for surface water in Maine (NAS 1977 WHO 1980) Tin

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

262 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-1 Conversion Between Mass on a Tin Basis to Mass on an Organotin Cation Basis

To convert from mass on a tin To Multiple by basis

mass on a TBT cation 244 basis mass on a DBT cation 196 basis mass on a MBT cation 148 basis

mass on a TMT cation 138 basis mass on a DMT cation 125 basis mass on a MMT cation 113 basis

mass on a TPT cation 295 basis mass on a DPT cation 230 basis mass on a MPT cation 165 basis

DBT = dibutyltin DMT = dimethyltin DPT = diphenyltin MBT = monobutyltin MMT = monomethyltin MPT = monophenyltin TBT = tributyltin TMT = trimethyltin TPT = triphenyltin

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

263 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

concentrations in public water supplies ranged from 11 to 22 microgL in 42 US cities and from 08 to

30 microgL in 32 of 175 water supplies in Arizona (NAS 1977 WHO 1980) Tin concentrations in drinking

water have been reported at lt10 microgL (WHO 2003) Tin is present in seawater at about 02ndash3 microgL (NAS

1977 WHO 1980) Tin concentration in fresh snow from the French Alps collected in 1998 at different

altitudes ranged from 157 to 436 pgg (Veysseyre et al 2001)

Concentrations of tributyltin (TBT) were found to range from 20 to 1800 ng TBTL in the Chesapeake

Bay area Maryland (Hall 1988) In surface waters from San Diego Bay California in 1986ndash1989

tributyltin levels averaged 47ndash13 ng TBTL in the north bay 13ndash99 ng TBTL in the south bay 35ndash

14 ng TBTL in US Navy pier regions and 19ndash120 ng TBTL in yacht harbors Tributyltin

concentrations in bottom waters in the San Diego Bay area ranged from 88 to 61 ng TBTL The mean

tributyltin concentrations in regional surface waters from Pearl Harbor Hawaii from 1986 to 1989 were

00ndash68 ng TBTL in channels 00ndash49 ng TBTL in outlying regions 24ndash31 ng TBTL in Southeast

Loch and 67ndash130 ng TBTL in a small marina Tributyltin concentrations in bottom waters in Pearl

Harbor ranged from 00 to 97 ng TBTL In Honolulu harbor surface and bottom water tributyltin

concentrations were 48ndash580 and 26ndash170 ng TBTL respectively (Grovhoug et al 1996) Tributyltin

concentrations in surface water from the harbor area of Osaka City Japan ranged from 2 to 33 ng TBTL

(Harino et al 1998) Butyltin compounds were detected in 32 of the 63 seawater samples (05 m depth)

that were collected from 18 areas along the Japanese coast from 1997 to 1999 Average butyltin

concentrations were 46 ng MBTL 45 ng DBTL and 68 ng TBTL from sampling stations for each of

the four areas the Pacific coast of northern Japan the coast along the Sea of Japan Tokyo Bay and the

adjacent area and western Japan The highest concentrations in these four areas were found in western

Japan with concentrations of 59 ng MBTL 69 ng DBTL and 201 ng TBTL (Takeuchi et al 2004)

The seasonal variations in tributyltin concentrations in marinas on Lake Ontario were studied from April

to December 1998 The marinas were at Toronto Mississauga Oakville Hamilton and Fifty Point

Canada Approximately 150ndash200 pleasure boats were in each marina in the summer Tributyltin

concentrations increased with increased boat activity with a maximum concentration of 14 ng SnL

reported in late August at Fifty Point Concentrations of tributyltin varied at the marinas peaking

between June and September but were always higher in the marinas compared to a reference site

Burlington Canada that was far from any marinas (Yang and Maguire 2000) Similar seasonal variations

were seen in seawater collected from marinas and harbors from southwestern Spain Tri- di- and

monobutyltin concentrations were significantly higher in water collected in May and August compared to

water collected in November and February The highest concentrations were found in waters in enclosed

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

264 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

areas with poor water turnover Tributyltin concentrations ranged from lt05 to 31 ng SnL Analysis for

phenyltin compounds was performed but none were found (Gomez-Ariza et al 2001)

While many studies reported on the occurrence of organotin compounds in marine environments fewer

studies reported the occurrence of organotin compounds in freshwater A study investigating the levels of

di- and tributyltin in fresh surface waters from nine sites across the United States found that at most sites

di- and tributyltin were not detected (detection limits were 970 and 180 ng butyltin ionL for dibutyltin

and tributyltin respectively) The highest dibutyltin concentrations were found in water sampled in 1998

from the Neuse River North Carolina and Contentnea Creek North Carolina at 140 and 160 ng DBTL

respectively Tributyltin was only detected in the Little Missouri River North Dakota and Flat River

North Carolina at concentrations of 265 and 600 ng TBTL respectively (Jones-Lepp et al 2004)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

agricultural activities Organotin compounds were detected in most water samples butyltin compounds

were most frequently detected with concentrations generally ranging from below the detection limit

(02 ng SnL) to 30 ng SnL Phenyltin compounds were also detected at concentrations generally ranging

from below the detection limit (02 ng SnL) to 20 ng SnL High phenyltin concentrations were detected

during the spring and the end of the summer and likely are derived from agricultural sources

Monophenyltin concentrations from over 400 up to 700 ng SnL were detected at four sampling sites

Octyltin compounds were detected as well however concentrations were generally lower ranging from

below the detection limit (02 ng SnL) to 15 ng SnL (Bancon-Montigny et al 2004)

Mono- and dimethyltin and mono- and dibutyltin compounds have been detected in Canadian drinking

water Drinking water in Canada is distributed through PVC pipes stabilized with methyl- and butyltin

compounds Methyl- and butyltin compounds were detected at concentrations up to 22 and 436 ng SnL

respectively in distributed water samples from six municipalities in Canada (Sadiki and Williams 1996)

Tap water in 10 of 22 homes collected in February 1995 from five Canadian municipalities contained

monomethyltin and dimethyltin compounds at concentrations of 05ndash257 and 05ndash65 ng SnL

respectively No organotin compounds were detected in the tap water from the other 12 houses No

organotin compounds were detected in raw water or in water just after leaving the treatment plant

suggesting that the source of these organotin compounds was from some component of the distribution

system (Sadiki et al 1996) Canadian drinking water samples collected during the winterndashspring 1996

from 28 sites and autumn 1996 from 21 sites were found to contain monomethyltin dimethyltin

monobutyltin and dibutyltin in ranges of lt05ndash2906 lt05ndash491 lt05ndash285 and lt05ndash523 ng SnL

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

265 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

respectively These compounds were detected with a frequency of 84 80 16 and 12 in the winterndash

spring survey and 100 57 7 and 7 in the autumn survey respectively A summer 1996 survey of

locations with the highest organotin concentrations in the winterndashspring survey showed a decrease in

mono- and dimethyltin concentration in 89 of the samples This finding was consistent with laboratory

studies that showed organotin release from PVC into water decreases after a few days PVC pipetubing

contains organotin compounds consistent with the organotin patterns found in the distributed water

samples Octyltin compounds which are not used as stabilizers in the PVC used to distribute drinking

water were not detected in drinking water samples Octyltin compounds are used instead as heat

stabilizers in PVC for food packaging Except for one treated water sample no organotin compounds

were detected in raw or treated water collected at the water treatment plant or in distributed water

supplied through polyethylene pipes (Sadiki and Williams 1999)

Organotin compounds were measured in precipitation and fog in the forested catchment in Northeast

Bavaria Germany during 2001ndash2002 Mono- di- and tri methyl and butyl derivatives as well as mono-

and dioctyltin compounds were detected in precipitation samples collected in this study The median total

organotin concentrations in bulk precipitation throughfall and fog were 583 146 and 571 ng SnL

respectively over the year-long monitoring study Monoalkyl tin compounds were the dominant species

found in precipitation with concentrations up to 192 ng SnL for monobutyltin in fog (Huang et al 2004)

643 Sediment and Soil

Tin concentrations in soil are generally low except in areas where tin containing minerals are present

(Bulten and Meinema 1991) Tin concentrations in the earths crust are approximately 2ndash3 mgkg

(Budavari 2001) Tin concentrations in soil can range from 2 to 200 mgkg but in areas of high tin

deposits levels of 1000 mgkg may occur (Schafer and Fembert 1984 WHO 1980) The mean

background soil concentration in the United States is 089 mgkg (Eckel and Langley 1988) Tin

concentrations in topsoil (0ndash76 cm) from the western end of East St Louis Illinois ranged from lt13 to

1130 mgkg East St Louis has a history of industrial facilities including smelters of ferrous and

nonferrous metals a coal-fired power plant chemical producing companies and petroleum refineries

(Kaminski and Landsberger 2000a) Sediment cores collected in January 1996 from Central Park Lake in

New York City New York contained average tin concentrations ranging from 40 mgkg at 44ndash47 cm

depth to 67 mgkg at 22ndash24 cm depth The average tin concentration in surface sediments (0ndash2 cm depth)

in Central Park Lake was 32 mgkg The similarities between the history of municipal solid waste

incineration in New York City and the accumulation of trace metals in the Central Park Lake sediments

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

266 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

appear to be consistent with incineration being the major source of several metals to the New York City

atmosphere (Chillrud et al 1999) Tin concentrations in sediments from the Wah Chang Ditch and the

northeast corner of Swan Lake an area that received runoff from a Texas tin smelter during the 1940s and

1950s were found to be as high as 8000 mgkg (Park and Presley 1997)

Organotin concentrations in sediment are summarized in Table 6-2 While tributyltin concentrations in

water have declined since restrictions on tributyltin use in paints have been in place concentrations of

tributyltin in sediments have remained relatively high Degradation of tributyltin in sediment is much

slower than in the water column Recent surveys of tributyltin concentrations in harbors and marinas in

various countries show concentrations ranging from hundreds of parts per billion (microgkg) to low parts per

million (mgkg) (Meador 2000) Tributyltin concentrations in sediment samples from the harbor area of

Osaka City Japan ranged from 0002 to 0966 mg TBTkg dry weight (Harino et al 1998) Sediment in

southwestern Spain during November 1993ndashFebruary 1994 and MayndashAugust 1994 were analyzed for the

presence of butyl- and phenyltin compounds No phenyltin species were found in sediment but mono-

di- and tributyltin were found at all stations sampled with concentrations of tributyltin ranging from

lt00006 to 016 mg Snkg dry weight Increased concentrations of organotin concentration during

summer months were not observed in the sediment as they were in water and biota and may be due to

vertical mixing of the sediment layers by natural and boating activities (Gomez-Ariza et al 2001) Tri-

di- and monobutyltin were detected in superficial sediment samples from five river estuaries (Deba

Urola Oria Oiartzun and Bidasoa) of Gipuzkoa North Spain at concentrations of 005ndash548 015ndash071

and 086ndash287 mg Snkg dry weight respectively Except for one sampling point monobutyltin a

degradation product of tributyltin accounted for the largest percentage of total butyltin (gt47)

(Arambarri et al 2003) Sediments collected in November 1997 from three sites near Nuuk Greenland

contained tributyltin concentrations ranging from lt0001 to 0171 mg Snkg dry weight (Jacobsen and

Asmund 2000) Tributyltin concentrations were measured in sediment collected in 1997 and 1999 from

transects along and perpendicular to the shipping lanes in the Sound (Oslashresund) and the

KattegatSkagerrak region an important shipping strait between Denmark and Sweden Tributyltin

concentrations ranged from 00015 to 00188 mg TBTkg dry weight in the Sound and were below the

detection limit (lt0001 mg TBTkg dry weight) in the Kattegat region A strong correlation was observed

between tributyltin concentration and the organic fraction in sediment samples from the Sound (Strand et

al 2003)

Bancon-Montigny et al (2004) reported a monitoring study involving sampling along 11 rivers in

southwest France from February to October 2001 Sites were chosen to represent specific industrial or

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

267 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Central-west Greenland near Nuuk Harbor surface sediment

TBT DBT MBT mg Snkg dw Mean Sandkaj 00097 00039 lt0001 Jacobsen and

Asmund 2000 Havnen 0171 00096 lt0001 Hundeoslashen lt0001 lt0001 lt0001

St Lawrence River in the Quebec City area surface sediments TBT DBT MBT DPT mg Snkg dw Mean Regoli et al 2001

Portneuf 0097 0286 0989 lt0001 Sillery 0146 0165 0087 lt0001 Quai Leacutevis 0173 0496 0123 0015 Bassin Louise 0888 0997 0203 lt0001 Outside Bassin 0807 0634 0185 lt0001 Louise St Charles River 0330 0579 0165 lt0001 St Lawrence Marina 0209 0389 0004 0101 Icircle dOrleacuteans East 0211 0045 0006 lt0001

Superficial sediments from five river estuaries (Deba Urola Oria Oiatzun and Bidasoa) of Gipuzkoa North Spain October 2000

TBT DBT MBT mg Snkg dw Range Arambarri et al 2003

005ndash548 015ndash071 086ndash287 Huelva coast southwest Spain

(November 1993ndash TBT DBT MBT mg Snkg dw Average Gomez-Ariza et February 1994) al 2001 Canela 00067 0017 00032 Pinillos 00009 00026 00015 Carreras River 00140 0080 0015 Idla Cristana harbor 0090 0090 0035 Cantil marina 0100 0270 0080 Punta Caiman 00028 00037 00012 Isla Cristina lt00006 lt00007 00034 breakwater (inner part) Terron harbor 280 460 450 Palo 20 36 80 Rompido marina 1300 400 240 Pino 08 07 09 Punta Umbria harbor 160 690 130

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

268 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-2 Organotin Levels in Sediment

Naturelocation of Concentration of organotin Reported sediment compound Units as Reference Six sites from the lowermost Tennessee River and Kentucky Lake United States surface sediments (0ndash5 cm)

MBT DBT TBT mgkg dwa Range Loganathan et al 1999

lt0003ndash lt0001ndash 00053ndash 0320 0014 0356

Thirteen sites in the Sound (Oslashresund) between Denmark and Sweden surface sediments 1997 NR NR 00015ndash mgkg dwa Range Strand et al

00188 2003 Twenty-four sites from Coddington Cove Newport Rhode Island United States surface sediments (0ndash2 cm) 1993 and 1994

NR NR 0032ndash0372 mg Snkg dw Range Wade et al 2004 Eighteen sites from 11 rivers in southwest France surface sediments July 2001

0016ndash 0001ndash 00013ndash mg Snkg dw Range Bancon-Montigny 0125 0087 0089 et al 2004

Eighteen sites from 11 rivers in southwest France surface sediments September 2001 0001ndash NDndash NDndash0020 mg Snkg dw Range Bancon-Montigny 0048 0037 et al 2004

aConcentration reported as mg butyltin ionkg sediment

DBT = dibutyltin DPT = diphenyltin dw = dry weight MBT = monobutyltin ND = not detected NR = no data reported SD = standard deviation TBT = tributyltin TPT = triphenyltin

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

269 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

agricultural activities Mono- di- and tributyltin were present in nearly all surface sediment samples

with concentrations ranging from 0001 to 0125 not detected to 0087 and not detected to

0089 mg Snkg dry weight respectively Mono- di- and triphenyltin and mono- di- and trioctyltin

were also detected in some sediment samples but with less frequency and generally at lower

concentrations than the butyltin compounds (Bancon-Montigny et al 2004)

Tri- di- and monobutyltin were detected in all sediment samples collected in the Quebec City harbor area

of the St Lawrence River with concentrations of 0097ndash0888 0045ndash0997 and 0004ndash0989 mg Snkg

dry weight respectively Diphenyltin was detected in two sites at concentrations of 0015 and 0101 mg

Snkg dry weight The organotin contamination found in this study was more comparable to levels

reported for Canadian marine harbor sites than to freshwater harbor sites (Regoli et al 2001) Tributyltin

and dibutyltin concentrations in surface sediments (0ndash2 cm) collected in 1990 and 1992 from intertidal

sites in Portland and Boothbay Harbor Maine ranged from 0024 to 124 mg TBTkg and from 0015 to

223 mg DBTkg dry weight (Page et al 1996) Tributyltin was detected in all 24 surface sediment (0ndash

20 cm) samples collected from Coddington Cove Newport Rhode Island on November 3 1993 and June

13 1994 concentrations ranged from 0032 to 0372 mg Snkg dry weight with a mean concentration of

0146 mg Snkg dry weight Sediment cores of varying depth (up to 18 cm) were obtained from seven

stations Tributyltin was detected in all of these samples and ranged from 00073 to 0225 mg Snkg dry

weight No consistent trends were observed in the tributyltin concentrations with depth suggesting that

mixing is an important process in the sediment column (Wade et al 2004) Kentucky Lake constitutes the

northernmost end of a shipping route for large barges and small ships between the Gulf of Mexico and the

Ohio River The lowermost Tennessee River receives industrial waste water from several industries in

the Calvert City Industrial Complex Total butyltin (BT) concentrations in the sediments of the

lowermost Tennessee River and Kentucky Lake ranged from 00068 to 0356 mg BTkg dry weight

(Loganathan et al 1999)

644 Other Environmental Media

Tin and tributyltin concentrations found in foods are summarized in Tables 6-3 and 6-4 respectively Tin

concentrations of vegetables fruits and fruit juices nuts dairy products meat fish poultry eggs

beverages and other foods not packaged in metal cans are generally lt2 mgkg Tin concentrations in

pastas and breads have been reported to range from lt0003 to 003 mgkg Mean tin concentrations

ranging from lt1 to 1000 mgkg have been found in foods packaged in unlacquered or partially lacquered

cans while the average tin concentration in foods in lacquered cans has been reported to be 0ndash69 mgkg

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

270 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Dietary intake in a French adult

Preserved foods in unlacquered cans Tomatoes (n=3) 84 (46ndash156) Mean range

Artichoke (n=1) 106

Mushrooms (n=3) 34 (24ndash45)

Pineapples (n=5) 82 (44ndash136)

Fruit cocktail (n=2) 97 (88ndash107) Peaches (n=3) 44 (27ndash71)

Pears (n=2) 47 (35ndash60) Apricot (n=1) 114

Stewed fruit (n=1) 30 Grapefruit (n=1) 128

Preserved foods in lacquered cans Bean (n=1) 24 Mean range Tomatoes (n=2) 60 (32ndash88) Asparagus (n=2) 39 (14ndash65) Garden peas (n=1) 10 Mushrooms (n=2) 69 (04ndash134) Apricot (n=1) 58 Cherry (n=1) 05 Strawberry (n=1) 06 Papaya (n=1) 29 Meats (n=4) 45 (11ndash94) Fishes (n=4) 07 (03ndash09)

Fresh foods Carrots (n=4) 008 (007ndash009) Mean range

Cabbage (n=1) 006

Endive (n=1) 01

Spinach (n=4) lt0003

Bean (n=1) 005

Leek (n=1) 003

Potatoes (n=5) 01 (01ndash02) Salad (n=4) 002 (001ndash003) Tomatoes (n=4) 005 (004ndash006) Lentils (n=2) 013 (009ndash017) Bananas (n=3) lt0003

Oranges (n=3) 007 (006ndash008) Pears (n=3) 007 (006ndash008) Apples (n=4) 004 (002ndash007)

Apricots (n=2) 007 (006ndash008) Alcoholic beverages (n=10) lt0003

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

271 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-3 Tin Levels in Fooda

Food item Concentration (mgkg) Reported as Mineral waters (n=5) lt0003 Nonalcoholic beverages (n=10) 004 (lt0003ndash013) Fishes and crustaceans (n=10) lt0003 Breads (n=6) lt0003 Pasta (n=12) lt0003 Meats (n=15) lt0003 Cooked pork meats (n=10) lt0003 Milk (n=10) lt0003 Dairy products (n=10) lt0003 Sugar (n=5) lt0003 Chocolate (n=1) lt0003 Oil (n=4) lt0003

aSource Biego et al 1999

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

272 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Seafood from eight markets worldwidea Reported as mean

Ulsan Korea

Mussel soft tissue 115

Shrimp whole body 33

Squid muscle 23

Shrimp tail only 19

Chub mackerel muscle 12

Flounder muscle 94

Marseille France

European squid muscle 655

European squid common cuttlefish elegant 376 cuttlefish muscle Mediterranean mussel soft tissue 87 Red tuna muscle 56 Common cuttlefish muscle 14 Elegant cuttlefish muscle 13 Green crab muscle 36 Lemon sole Senegalse sole muscle Not detected

Galveston Texas United States Pacific oyster American oyster soft tissue 72 Squid muscle 16

Shrimp whole body 12

Shrimp tail only 11

Southern flounder tropical flounder muscle 6 Oyster soft tissue 46

Blue runners Atlantic bonito muscle 45 Singapore

Mackerel muscle 23

Bigeye tuna muscle 20

Mitre squid muscle 12

Short-necked clam soft tissue 56 Indian halibut muscle 39

Crab muscle 31

Silver pomfret muscle 28

Stockholm Sweden

Atlantic herring muscle 36

Common mussel blue mussel soft tissue 22 European eel muscle 28

Plaice muscle 25

Atlantic salmon muscle Not detected

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

273 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Concentration (ng TBTg) wet weight Sydney Australia

Slimy mackerel muscle 13

Sydney rock oyster soft tissue 92 Butterfly fan lobster muscle (tail) 72 Arrow squid cuttlefish muscle 7 Tiger flathead muscle 6

Yellowtail kingfish muscle 53

Largetooth flounder muscle 42

Halifax Canada

Longfin inshore squid muscle 89 Cock shrimp whole body 77

Common mussel soft tissue 56 Witch flounder muscle 27

Atlantic salmon muscle Not detected

Cock shrimp tail only Not detected London England

Oyster soft tissue 43

Shrimp muscle 139

Atlantic herring muscle 11

Squid muscle 79

Mackerel muscle 73

Mussel soft tissue 59

Seafood from six markets in the United Statesb Reported as mean summer winter San Pedro California

Bottom fish 71 17

Crustaceans 12 11

Mollusks 13 15

Pensacola Florida

Bottom fish 21 14

Crustaceans 10 14

Mollusks 20 no data

Chicago Illinois

Freshwater fish 59 32

Boston Massachusetts

Bottom fish 13 12

Mollusks 31 070

Baltimore Maryland

Bottom fish 13 23

Crustaceans 12 10

Mollusks 33 054

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

TIN AND TIN COMPOUNDS 274

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-4 Tributyltin (TBT) Levels in Food

Food item Seattle Washington

Bottom fish Crustaceans Pen-reared fish

Concentration (ng TBTg) wet weight

098 10 24 12 52 14

aKeithly et al 1999 bCardwell et al 1999b

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

275 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

(WHO 2003) Data from the Can Manufacturers Institute (CMI 1988) indicate that gt90 of tin-lined

cans used for food today are lacquered Only light colored fruit and fruit juices are packed in unlacquered

cans since tin helps maintain the color of the fruit Tin content in foods stored in opened metal cans

increases over time since tin can rapidly dissolve in the presence of oxygen Acidic foods are more

aggressive to the tin coating in metal cans and canned acidic foods have higher tin contents Tin

concentrations of canned foods increase with storage time and temperature (WHO 2003)

Tin concentrations in various foods were determined in a dietary tin intake study for adults in France

Foods in lacquered cans generally were found to contain tin concentrations below 10 mgkg and tin

concentrations ranged from 24 to 156 mgkg in food from unlacquered cans The average tin

concentration in fresh foods was 003 mgkg (Bieacutego et al 1999) Canned vegetables and fruit products

were found to have mean tin concentrations of 44 and 17 mgkg fresh weight respectively in a 1994 total

diet study in the United Kingdom (Ysart et al 1999) A study of metal concentration in canned milk

products in Lithuania showed that the content of tin in canned milk exceeded the concentration in raw

milk which in 1990ndash1992 was on average 022 mgkg Mean tin concentrations in evaporated sterilized

milk concentrated sterilized milk and sweetened condensed milk were 85 89 and 40 mgkg

respectively Tin concentrations in canned milk were shown to increase during storage (Ramonaiytė

2001) Local and imported edible seaweeds obtained in British Columbia were found to contain tin in

concentrations ranging from 001 to 046 mgkg dry weight (van Netten et al 2000)

Samples of fish crustaceans cephalopods (ie squid) and bivalve mollusks were purchased from

markets in Stockholm Sweden London England Marseille France Singapore Ulsan Korea Sydney

Australia Galveston United States and Halifax Canada during August and September 1997 and

analyzed for tributyltin content Average tributyltin concentrations for bivalves pelagic fish pelagic

invertebrates and flatfish were 40 16 74 and 46 microg TBTkg respectively It was noted that the high

concentrations in bivalves were expected The lower concentrations of tributyltin found in flatfish were

unexpected since flatfish live on sediment and consume mostly benthic prey Sediment is considered a

sink for tributyltin in aquatic environments (Keithly et al 1999) In a similar study seafood was

purchased in August 1989 and January 1990 representing a summer and winter sample from Boston

Massachusetts Baltimore Maryland Seattle Washington Pensacola Florida San Pedro California and

Chicago Illinois These locations represented major fishing and aquaculture areas on the coasts of the

United States and the Great Lakes Categories of seafood sampled were bottom fish crustacea

freshwater fish mollusks and maricultured fish Tributyltin was detected in 35 of samples analyzed

Seafood purchased during the summer was found to have slightly higher tributyltin concentrations

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

276 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

compared to seafood purchased in the winter in 10 of the 15 instances where the same or similar species

were sampled from the same location during the summer and winter surveys Elevated tributyltin

concentrations in seafood sampled during the summer were believed to be consistent with increased

recreational boat activity in the summer Mean tributyltin summer concentrations for bottom fish

crustaceans and mollusks were 098ndash71 10ndash24 and 20ndash13 microg TBTkg respectively Mean tributyltin

winter concentrations for the same seafood categories were 10ndash23 10ndash14 and 054ndash63 microg TBTkg

respectively The respective summer and winter mean concentrations of tributyltin were 59 and 32 microg

TBTkg in freshwater fish from Chicago Illinois and 52 and 14 microg TBTkg for pen-reared fish from

Seattle Washington (Cardwell et al 1999b)

Tributyltin and triphenyltin concentrations were determined in foods in a market basket study About

100 kinds of foods were purchased every year in 1990ndash1993 in Shiga Prefecture Japan Foods were

divided into 13 groups I rice II cereals grains and potatoes III sugar and cakes IV fats and oils V

bean products VI fruits VII green vegetables VIII other vegetables and seaweeds IX seasonal

beverages X fish mollusks and crustaceans XI meats and eggs XII milk and dairy products and XIII

cooked meats (curry and hash) Tributyltin and triphenyltin (TPT) were only detected in group X (fish

mollusks and crustaceans) and group VIII (vegetables and seaweeds) with higher levels in group X

(52 microg TBT and 04 microg TPT) than in group VIII (02 microg TBT and 0 microg TPT) (Tsuda et al 1995)

Twenty-two samples of gin martini cognac red wine and sherry that were stored in plastic containers

used in Canada for storage of alcoholic beverages were analyzed for dioctyltin compounds dioctyltin

bis(maleate) and dioctyltin SS-bis(isooctyl mercaptoacetate) Beverages tested contained lt40 microgL tin

While these plastic containers contained up to 1700 microg Sng and these dioctyltin compounds were

soluble in alcohol (647 and 150 microgmL respectively) there was no evidence of leaching in any samples

analyzed (Meacuteranger 1975)

Tin and organotin concentrations found in human tissues and fluids are summarized in Table 6-5 Tin

was detected in nine human adipose tissue samples during the 1982 National Human Adipose Tissue

Survey at concentrations ranging from 46 to 15 microgg (Stanley 1986) Urine samples were selected from

the available archived urine specimens from participants in the National Health and Nutrition

Examination Survey (NHANES) III conducted from 1988 to 1994 The 500 samples were chosen to

represent a broad range of the US population Tin was detected in 89 of samples (detection limit

01 microgL) and had a 95th upper percentile concentration of 201 microgL (Paschal et al 1998) Tissue samples

from various organs were obtained from 20 deceased individuals (15 men and 5 women) who at the time

of their death lived in Terragona Spain and the surrounding areas for at least 10 years No known

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

277 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-5 Tin and Organotin Levels in Human Tissues and Fluids

Human tissue or fluid Concentration Units Reported as Reference Tin Adipose tissue (n=9) 46ndash15 microgg Range Stanley 1986 Urine NHANES (n=500) 201 microgL 95th upper Paschal et al 1998

percentile Urine (n=14) occupationally 18 (10ndash27) microgL Mean (range) Schramel et al 1997 non-exposed men and women Germany Terragona Spain (n=20)

Brain 098 (028ndash457) microgg ww Mean (range) Llobet et al 1998 Bone 618 (272ndash1732) Kidney 154 (068ndash304) Liver 444 (184ndash1016) Lung 174 (067ndash654)

Terragona Spain (n=78) Brain 027 (023ndash074) microgg ww Mean (range) Garciacutea et al 2001 Bone 047 (045ndash076) Kidney 025 (023ndash043) Liver 016 (009ndash027) Lung 024 (023ndash031)

Organotin compounds Blood (n=32)

Central Michigan Monobutyltin 000817 microgmLa Mean Kannan et al 1999 Dibutyltin 000494 Tributyltin 000818

Liver Poland (n=9)

Total butyltin 00024ndash00110 microgg wwa Range Kannan and Falandysz (MBT+DBT+TBT) 1997

Denmark (n=18) Monobutyltin 00003ndash00047 microgg wwa Range Nielsen and Strand

2002 Dibutyltin 00008ndash00283 Tributyltin lt00003 Triphenyltin lt0003

Japan (n=4) Monobutyltin 0018 (0012ndash0022) microgg wwa Mean (range) Takahashi et al 1999 Dibutyltin 0066 (0045ndash0078) Tributyltin lt00020

aConcentrations of organotins are reported in microg organotin speciesg or mL

DBT = dibutyltin MBT = monobutyltin TBT = tributyltin ww = wet weight

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

278 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

occupational exposure to metals was found for these subjects based on a questionnaire sent to relatives

Tin concentrations were lowest in brain tissue and highest in bone at 098 and 618 microgg wet weight

respectively No significant differences in tin concentrations were noted based on gender or age (Llobet

et al 1998) In a similar study samples of liver lung kidney brain and bone were collected from

78 adult subjects (57 men and 21 women) autopsied between 1997 and 1999 who at the time of death

lived in Tarragona County Spain or in the surroundings for the last 10 years Autopsy records included

data on gender age occupation residence and smoking and drinking habits No occupational exposure

to heavy metals was found in this group Ages ranged from 36 to 76 years 55 were considered

smokers and 24 were considered drinkers An individual was considered a smoker if he or she smoked

more than one pack of cigarettes per day for at least 1 year of his or her life Men who consumed more

than 280 g of alcohol per week (168 g for women) were considered drinkers Place of residence was

divided into three areas (a) near the petrochemical industry (b) near the petroleum refineries and

municipal solid waste incinerator and (c) urban area (downtown) For tin concentrations in the tissues

studied no significant differences between sex smoking and drinking habits or places of residence were

found One exception was in the kidney where tin concentrations were slightly higher in drinkers (Garciacutea

et al 2001)

Butyltin compounds were measured in human blood collected in July 1998 in central Michigan from

17 male and 15 female individuals Mono- di- and tributyltin were detected in 53 81 and 70 of the

samples Mono- di- and tributyltin concentrations ranged from below the detection limit to maximum

concentrations of 0027 0016 and 0085 microg organotin ionmL respectively Total butyltin

concentrations ranged from below the detection limit to 0101 microg BTmL (Kannan et al 1999) Human

liver samples from nine individuals aged 45ndash83 obtained from the Gdansk School of Medicine Poland

in March 1994 were found to contain total butyltin (mono- di- and tributyltin) concentrations ranging

from 00024 to 0011 microg BTg wet weight (Kannan and Falandysz 1997) Four human liver samples

obtained by autopsy in Ehime University Hospital Japan in 1997 and 1998 were found to contain average

concentrations of mono- di- tributyltin and total butyltin of 0018 0066 lt0002 and 0084 microg

organotin iong wet weight respectively (Takahashi et al 1999) Liver samples from 18 deceased Danish

men aged 21ndash82 were collected from December 1999 to January 2000 at the Institute for Forensic

Medicine SDU Odense University Concentrations of tributyltin and triphenyltin were all below the

detection limit lt00003 microg TBTg and lt0003 microg TPTg Mean concentrations (and ranges) of mono-

and dibutyltin were 00016 (00003ndash00047) microg MBTg and 0009 (00008ndash00283) microg DBTg wet weight

A large interperson variability was noted for this sample with a more than 25-fold difference between the

lowest and highest dibutyltin liver concentration (Nielsen and Strand 2002)

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

279 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Ten individual indoor dust samples were collected from 10 regions from the United Kingdom in 2002

Samples were collected primarily from private households but also included some businesses Samples

were analyzed for various chemicals including eight organotin compounds mono- di- tri- and

tetrabutyltin mono- and dioctyltin tricyclohexyltin and triphenyltin Mono- di- and tributyltin and

mono- and dioctyltin were found in all pooled regional samples and mean concentrations were 1375

0563 01445 04506 and 01292 microg organotin iong respectively Triphenyltin was found in only one

pooled sample at a concentration of 00069 microg TPTg Tetrabutyltin and trihexyltin were not detected

Detection limits were 0001 microg organotin iong dry weight Possible sources of these organotin

compounds in the home may be from the use of butyl- and octyltin compounds as stabilizers in PVC In

addition tributyltin is used as a fungicide and as treatment against dust-mites in carpets and textiles Dust

samples from Denmark Finland France Spain and Sweden showed similar patterns of organotin

contents as found in the United Kingdom samples (Santillo et al 2003)

Tin concentrations in the kidneys of mink collected from the Kootenay River and lower Fraser River in

British Columbia Canada were 625 and 55 microgg dry weight Tin concentrations in the livers of mink

from the upper and lower Fraser River were 553 and 517 microgg dry weight respectively Tin

concentrations in the livers of otters were lt4 microgg dry weight collected from the Kootenay lower and

upper Columbia and upper Fraser Rivers and 267 microgg from the lower Fraser River (Harding et al

1998) Tin concentrations in mantle muscle and liver samples of juvenile Japanese common squid

Todarodes pacificus collected from three locations in and near Japanese coasts were 0042ndash0050 and

0077ndash013 microgg wet weight respectively (Ichihashi et al 2001)

Concentrations of butyltin (mono- di- and tributyltin) compounds were determined in the kidney and

liver of 18 species of seabirds collected between the mid-1980s and mid-1990s from Japan Korea the

North Pacific Ocean and the southern Indian Ocean The highest mean total butyltin concentrations were

found in the kidney and liver of inland and coastal birds The highest mean concentrations of butyltins

(BT) were found in common cormorants from Lake Biwa Japan at 0300 and 0280 microg BTg wet weight

in kidney and liver respectively Among the open sea birds the Laysan albatross from the North Pacific

Ocean had the highest total butyltin concentrations in the liver at 0043 microg BTg wet weight (Guruge et al

1997)

Concentrations of tributyltin and triphenyltin were measured in the muscle of 11 species of fish from the

Port of Osaka and Yodo River Japan Concentrations of tributyltin and triphenyltin were found ranging

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

280 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

from 0011 to 0182 microg TBTg and from lt0001 to 0130 microg TPTg wet weight In addition mono- and

dibutyltin and diphenyltin were detected in all samples Monophenyltin was detected in all but one

sample from the Port of Osaka and none of the samples from the Yoda River (lt0001 microg MPTg wet

weight) Concentrations of organotin compounds were higher in fish from sea areas than those from the

river (Harino et al 2000) Ueno et al (2004) determined butyltin concentrations in the liver of skipjack

tuna (Katsuwonus pelamis) collected from Asian offshore waters off-Seychelles (west African coast)

off-Brazil (west South American coast) and in open seas (North Pacific) during 1996ndash2001 High

concentrations of butyltins were found in skipjack tuna from offshore waters around Japan with

concentrations up to 0400 microg BTg wet weight Tributyltin was detected a relatively higher

concentrations in all locations with mean concentrations ranging from 00049 to 0200 microg TBTg wet

weight in the North Pacific and the East China Sea respectively Monobutyltin concentrations were

below the detection limit (00018 microg MBTg) for four samples from the South China Sea off-Indonesia

off-Seychelles and off-Brazil and ranged up to 0017 microg MBTg wet weight in the East China Sea (Ueno

et al 2004)

Concentrations of di- and tributyltin were studied in whole-body fish samples from six freshwater sites

across the United States (Jones-Lepp et al 2004) Di- and tributyltin were not detected in 8 and 9 of the

13 fish samples respectively that were collected from these sites (detection limits were 000097 and

00018 microgg for di- and tributyltin respectively) The highest concentrations were reported in largemouth

bass (Micropterus salmoides) from Red Bank Creek South Carolina at 0221 microg DBTg and in

shorthead rosehorse (Moxostoma macrolepidotum) from the Little Missouri River North Dakota at

0389 microg TBTg (Jones-Lepp et al 2004)

Strand and Asmund (2003) studied the concentrations of butyltins in bivalves collected between 1999 and

2000 from six areas along the west coast of Greenland The highest tributyltin concentration 0254 microg

TBTg wet weight was found in mussels (Mytilus edulis) sampled inside Nuuk harbor the largest harbor

in West Greenland Tributyltin could only be detected in two of the six areas outside of the harbor areas

at concentrations of 0001 and 00027 microg TBTg wet weight in Chlamys islandica and Nuculana pernula

respectively Di- and monobutyltin concentrations ranged from lt00005 to 0025 and from lt00005 to

00041 microg organotin iong wet weight respectively in M edulis in the harbor sites Di- and monobutyltin

were not detected in C islandica from open water sites and were detected in N pernula from open water

at 00016 and 00012 microg organotin iong wet weight respectively Triphenyltin could not be detected in

any samples (lt0005 microg TPhTg wet weight) (Strand and Asmund 2003) M edulis clams (Mercenaria

mercenaria) and fish (Tautogolabrus adspersus) collected in 1995 from Coddington Cove Newport

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

281 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Rhode Island were found to contain tributyltin concentrations ranging from 00092 to 0977 microg Sng wet

weight Tributyltin concentrations in lobsters from the same area were all below the detection limit

(lt0006 microg Sng) (Wade et al 2004) Tributyltin concentrations were measured in benthic mollusks

(N pernula Nucula sulcata Nucula tenuis Artica islandica Musculus niger Cardium echinatum

Buccinum undatum and Neptunea antiqua) collected in 1997 and 1999 from transects along and

perpendicular to the shipping lanes in the Sound (Oslashresund) and the KattegatSkagerrak region an

important shipping strait between Denmark and Sweden Di- and tributyltin were detected in all mollusk

samples and ranged from 0011 to 0267 microg DBTg and from 00081 to 1316 microg TBTg dry weight

(Strand et al 2003) Tributyltin was found in mussels (Mytilus galloprovincialis) from Portuguese coastal

waters at concentrations of 0011ndash0789 microg Sng dry weight and was detected at all 17 sites sampled

between May and July 2000 Mono- and dibutyl tin were also found in most samples with concentrations

ranging from not quantifiable to 0605 and from not quantifiable to 0345 microg Sng dry weight

respectively Di- and triphenyltin concentrations were not quantifiable in all but one sample with a

triphenyltin concentration of 0016 microg Sng dry weight (Barroso et al 2004)

Tributyltin dibutyltin and monobutyltin concentrations were determined in the liver kidney and brain

tissues of adult southern sea otters (Enhydra lutris nereis) found dead along the coast of California during

1992ndash1996 The mean and range of liver kidney and brain concentrations for total butyltin compounds

were 1320 (0040ndash92) 0160 (0004ndash043) and 0061 (00027ndash014) microg BTg wet weight respectively

The accumulation of butyltin compounds in sea otters was explained by their bottom-feeding habit and a

diet that consists exclusively of invertebrates such as mollusks and gastropods (Kannan et al 1998a)

Butyltin concentrations in the liver kidney and brain tissues of southern sea otters (E lutris nereis) found

dead on the California coast during 1992ndash1996 were 0040ndash53 0004ndash0265 and 00039ndash0140 microg BTg

wet weight respectively (Kannan et al 2004)

Berge et al (2004) studied the concentrations of organotin compounds in samples of harbor porpoise

(Phocoena phocoena) common seal (Phoca vitulina) ringed seal (Phoca hispida) and glaucous gull

(Larus hyperboreus) from Norwegian territories without any obvious point sources of tributyltin Most

samples were collected between 1998 and 2000 however some of the porpoise samples were collected in

1988 which is prior to the restriction on the use of tributyltin on smaller boats The highest

concentrations of mono- di- and tributyltin were found in harbor porpoise samples in Northern Norway

in 1988 especially in liver tissue with mean concentrations of 00345 0285 and 0098 microg Sng wet

weight respectively In general mono- di- and tributyltin concentrations were lower in harbor porpoise

tissues sampled in 1999 than in 1988 No phenyltins were found in ringed seals from Spitsbergen or in

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

282 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

glaucous gulls from Bear Island Concentrations of phenyltins in blubber kidney and brain of common

seals were below the detection limit (generally lt0001 microg Sng wet weight) Mono- di- and triphenyltin

were detected in the liver muscle and kidney of harbor porpoises samples in 1999 mono- and

diphenyltin were dominant in liver and muscle with mean concentrations of 00164 and 00192 microg Sng

wet weight respectively (Berge et al 2004)

Ciesielski et al (2004) measured the organotin concentrations in liver tissue of marine mammals found

between 1999 and 2003 from the Polish coast of the Baltic Sea The mammals studied included 14 harbor

porpoises (P phocoena) 2 striped dolphins (species not specified) 1 ringed seal (P hispida) and 2 grey

seals (Halichoerus grypus) Tributyltin was detected in all samples and ranged from 0044 to 1488 microg

Sng dry weight in grey seal and striped dolphin respectively Dibutyltin was not detected in the two

grey seal liver samples but was detected in all other samples ranging from 0071 to 3295 microg Sng dry

weight in ringed seal and striped dolphin respectively Monobutyltin was not detected in one of the grey

seal samples but was detected in all other samples ranging from 0021 to 2915 microg Sng dry weight for

grey seal and striped dolphin respectively (Ciesielski et al 2004)

65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE

Human exposure to tin may occur by inhalation ingestion or dermal contact However exposure of the

general population occurs primarily by ingestion of food (NAS 1977 WHO 1980) The daily intake from

air is unlikely to exceed 05 microg based on concentrations of tin in air that have been estimated to be in the

range of 0002ndash003 microgm3 (Bieacutego et al 1999) Tinplate which is steel coated with a thin layer of

metallic tin has been used to line cans for food Some of these cans are also coated with a lacquer

While new canning techniques have decreased the amount of tin contamination of foods over the years

metal cans still are the main source of tin in the diet (WHO 2003) Tin(II) chloride is used as a food

additive and has US FDA Generally Regarded As Safe (GRAS) approval It is used as a preservative for

canned soda water a color retention agent in canned asparagus and a component in food packaging

materials (Kroschwitz and Howe 1997) Tin exposure may occur from dental preparations since tin(II)

fluoride (041) is an approved fluoride source in dentifrices (Pader 1993) In a laboratory study to

determine the amount of tin and other metals leached into water from copper piping with four types of

lead-free solders which contain 94ndash955 tin no significant leaching of tin was observed (Subramanian

et al 1991)

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

283 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Estimates of daily dietary tin intake ranged from 1 mg for diets consisting mainly of fresh meats

vegetables and cereals to 38 mg for diets including a high proportion of canned foods (Schafer and

Femfert 1984 WHO 1980) The average daily tin intake of an adult in the United States was estimated at

4003 mg (4 mg from food and 0003 mg from air) and with undetectable levels contributed by drinking

water (EPA 1987a WHO 1980) Other estimates of human daily intake range from 02 to 17 mg

(Klaassen et al 1986 Krigman and Silverman 1984) Tin levels in drinking water have been reported at

lt0010 mgL If daily intake of water is assumed to be 2 Lday then intake of tin from water would be

0012ndash0020 mgday (WHO 2003) The tin contents in fresh food or food packaged in lacquered or

unlacquered cans were determined to estimate the daily tin intake in an adult in France From this study

it was found that canned foods while representing 6ndash7 of the daily consumed foods represented gt95

of the total tin intake The estimated tin intake by an adult in France was determined to be 004 mgkg

body weight (Bieacutego et al 1999) In a 1994 total diet study in the United Kingdom the canned vegetables

group and fruit product group contributed 66 and 31 respectively to the total average exposure of tin

which was estimated as 24 mgday From this study an upper range exposure to tin of 79 mgday was

estimated Population dietary exposure to tin from total diet studies in the United Kingdom from 1976 to

1994 ranged from 17 mgday in 1985 to 54 mgday in 1991 (Ysart et al 1999)

Little is known about the extent of exposure of humans to butyltin compounds (Kannan et al 1999)

Occupational exposure represents the greatest exposure to tributyltin nonoccupational exposure to

tributyltin is usually slight with diet as the most important means of exposure (Demora and Pelletier

1997) Dermal absorption is a significant route of occupational exposure for certain organotin

compounds (Stewart and Lassiter 2001) Household commodities made of polyurethane plastic

polymers and silicons contain butyltin concentrations in the ppm range Butyltin compounds are also

found in seafood (Cardwell et al 1999b Kannan et al 1999 Keithly et al 1999) The daily intakes of

tributyltin and triphenyltin in Japan were estimated to be 47 and 07 microg in 1991 and 22 and 07 microg in

1992 respectively based on a duplicate portion study In this study cooked meals were collected for

3 days from women in Shiga Prefecture Japan in 1991 and 1992 and were homogenized and frozen In a

separate market basket study in Shiga Prefecture Japan daily intakes of tributyltin and triphenyltin in

Japan were estimated to be 69 and 54 microg in 1991 and 67 and 13 microg in 1992 respectively Of the food

groups analyzed in the market basket study 95 of the daily intakes of tributyltin and triphenyltin came

from the fish mollusks and crustaceans food group (Tsuda et al 1995) Human dietary exposure to

butyltins by food in order of importance may be regarded as marine food gt animal-origin foods (dairy

and meat) gt farm products (rice and sunflower and peanut oil) (Kannan et al 1995) Other routes of

exposure to organotin compounds may include leaching of organotin compounds from PVC and related

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

284 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

materials which have led to contamination of food drinking water and municipal sewage sludges as

suggested in some studies Dibutyltin and octyltin compounds have been found in some textiles products

It has been demonstrated that butyltin compounds in siliconized baking parchment can be transferred to

food baked on this type of baking parchment (Takahashi et al 1999) Organotin compounds were found

in household dust in a UK study (Santillo et al 2003)

Occupational exposures to tin may be substantial Inhalation or dermal exposure to triphenyltin leachate

used in fungicides and insecticides may occur during both manufacturing and application (NAS 1977

WHO 1980) Workers in the numerous industries producing or using inorganic tin or organotin

compounds (Section 53) may also be exposed NIOSH estimated that 730000 workers in the United

States were potentially exposed to tin in the workplace in 1980 (NOES 1989) The National Occupational

Exposure Survey (NOES) database does not contain information on the frequency concentration or

duration of exposure to workers to tin or any of its compounds These surveys provide only estimates of

number of workers potentially exposed to chemicals in the workplace

66 EXPOSURES OF CHILDREN

This section focuses on exposures from conception to maturity at 18 years in humans Differences from

adults in susceptibility to hazardous substances are discussed in Section 37 Childrenrsquos Susceptibility

Children are not small adults A childrsquos exposure may differ from an adultrsquos exposure in many ways

Children drink more fluids eat more food breathe more air per kilogram of body weight and have a

larger skin surface in proportion to their body volume A childrsquos diet often differs from that of adults

The developing humanrsquos source of nutrition changes with age from placental nourishment to breast milk

or formula to the diet of older children who eat more of certain types of foods than adults A childrsquos

behavior and lifestyle also influence exposure Children crawl on the floor put things in their mouths

sometimes eat inappropriate things (such as dirt or paint chips) and spend more time outdoors Children

also are closer to the ground and they do not use the judgment of adults to avoid hazards (NRC 1993)

Exposure to tin and tin compounds for children will be similar to adults and will occur primarily through

the diet In a 7-day duplicate diet study of 97 pre-school aged (175ndash22 years) children from the

Birmingham area in the United Kingdom the average daily intake of tin was 178 mgkg In this study

mothers were asked to collect and weigh duplicate samples of all food and drink (including water)

consumed by their children in and outside of the home There was a significant correlation between the

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

285 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

amount of canned food consumed and the concentration of tin in the diet (Smart et al 1987) Children

living in institutional settings may be served more canned foods due to their ease of storage and

economical price and may be exposed to higher levels of tin than the general population (WHO 2003)

In a joint World Health Organization (WHO) and International Atomic Energy Agency (IAEA)

collaborative study published in 1989 on minor and trace elements in breast milk median tin

concentrations were 281 and 024 microgL in breast milk from women in Guatemala and Zaire respectively

3 months after giving birth (WHOIAEA 1989) No data were located regarding current concentrations of

tin or tin compounds in human breast milk in the United States Other possible exposures to tin by

children may occur from the clothing of other household members with occupational exposure (Rinehart

and Yanagisawa 1993)

67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES

People eating a high percentage of their diet from canned foods will be exposed to higher amounts of tin

than the general population For example people living in intuitional settings such as nursing homes

boarding schools or prisons or people with lower incomes may be served or choose canned foods due to

their ease of storage and economical price (WHO 2003)

Potentially high inhalation exposures to tin and its compounds may occur in the workplace or from

agricultural uses of tin compounds A study of the tin and lead concentrations in house dust from the

homes of nine electrical-cable splicers employed by a large power company found higher tin

concentrations in house dust from the splicers homes compared to house dust from control homes Tin

concentrations in house dust from the homes of splicers and the controls were 117 and 14 ppm in laundry

areas and in other areas concentrations were 66 ppm and not detected (lt10 ppm) respectively In one of

the control homes occupied by a person who soldered copper water pipes in his home using lead-tin

solder tin concentrations in dust were 5 times higher than levels found in dust from homes of either the

control or splicer groups (Rinehart and Yanagisawa 1993) In a 1994 study of heavy metal exposure in a

Bolivian smelter personal breathing zone air samples were collected by 15 workers representing 12 job

categories during one shift according to NIOSH Method 7300 Tin exposure was below the occupational

exposure criterion and was considered not hazardous (Sussell et al 1996)

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

286 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

68 ADEQUACY OF THE DATABASE

Section 104(i)(5) of CERCLA as amended directs the Administrator of ATSDR (in consultation with the

Administrator of EPA and agencies and programs of the Public Health Service) to assess whether

adequate information on the health effects of tin and tin compounds is available Where adequate

information is not available ATSDR in conjunction with NTP is required to assure the initiation of a

program of research designed to determine the health effects (and techniques for developing methods to

determine such health effects) of tin and tin compounds

The following categories of possible data needs have been identified by a joint team of scientists from

ATSDR NTP and EPA They are defined as substance-specific informational needs that if met would

reduce the uncertainties of human health assessment This definition should not be interpreted to mean

that all data needs discussed in this section must be filled In the future the identified data needs will be

evaluated and prioritized and a substance-specific research agenda will be proposed

681 Identification of Data Needs

Physical and Chemical Properties Table 4-2 and Section 42 summarize many of the relevant

physical and chemical properties of tin and many of its compounds There are adequate data for the

physical and chemical properties of tin and inorganic tin compounds The chemical behavior of most of

the common organotin compounds in environmentally-relevant media is not well known There is a need

to measure the solubility and vapor pressure of the more important organotin compounds in order to

provide a more reliable basis for predicting their fate in the environment

Production ImportExport Use Release and Disposal According to the Emergency

Planning and Community Right-to-Know Act of 1986 42 USC Section 11023 industries are required

to submit substance release and off-site transfer information to the EPA The TRI which contains this

information for 2001 became available in May of 2004 This database is updated yearly and should

provide a list of industrial production facilities and emissions

Production volumes and uses of tin are well-documented (Carlin 2003b 2004) While data were

available on the uses of many organotin compounds current production volumes could not be located

Data on releases disposal practices and possible environmental contamination from uses of tin and its

compounds are limited Since tin is not on the TRI and is not listed as an EPA hazardous waste

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

287 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

constituent current data are not available on industrial releases or disposal practices Information on

releases or disposal practices and current quantitative data on leaching of inorganic and organic forms of

tin into foods from tin-lined cans and PVC packaging materials would be useful in assessing potential

human exposure to tin compounds

Environmental Fate From the information available it appears likely that both inorganic and

organotin will partition to soils and sediments and will not volatilize from water (Blunden et al 1984

Cooney 1988 Fent 1996 Maguire et al 1983 1985 WHO 1980) Research on physical and biological

processes in water and at sediment-water interfaces would be particularly helpful to more accurately

predict the fate of tin compounds released to the environment Methyltin compounds can be produced in

the environment by biomethylation of inorganic tin (Fent 1996) It has been suggested that methylation

of butyltin compounds in sediment may lead to mobilization of tin species into the water column and

possibly to the atmosphere However there is currently no significant evidence of losses of organotin

compounds to the atmosphere (Amouroux et al 2000)

Bioavailability from Environmental Media Inorganic tin is not well absorbed after inhalation

oral and dermal exposure Organotin compounds are somewhat better absorbed by both the inhalation

and oral routes (Hiles 1974 Mori et al 1984) Dermal absorption is a significant route of occupational

exposure for certain organotin compounds (Stewart and Lassiter 2001) The daily intakes of tin from air

food and water are small (WHO 1980) Further study of human intake of organotin compounds from

food and water would also be useful The pH may be an important consideration for the bioavailability of

organotin compounds Bioconcentration studies by Looser et al (1998) indicated that as pH increases

uptake of organotin compounds increases

Food Chain Bioaccumulation It has been established that organotins can be bioconcentrated by

aquatic organisms in marine environments (Gomez-Ariza et al 2001 Harino et al 2000 Hongxia et al

1998 Laughlin and Linden 1985 Looser et al 1998 Maguire et al 1984 Meador 2000 Suzuki et al

1998 Tsuda et al 1986 Waldock and Thain 1983 Yamada and Takayanagi 1992) Similar information

for terrestrial ecosystems would be useful Inorganic tin compounds may also be bioconcentrated but

data are limited (Seidel et al 1980 Thompson et al 1972) There is no information available on the

potential transfer of inorganic tin or organotin compounds from lower trophic levels to higher levels

This information would be useful because studies have shown that organotin can be bioconcentrated

significantly

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

288 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposure Levels in Environmental Media Reliable monitoring data for the levels of tin and tin

compounds in contaminated media at hazardous waste sites are needed so that the information obtained

on levels of tin and tin compounds in the environment can be used in combination with the known body

burden of tin and tin compounds to assess the potential risk of adverse health effects in populations living

in the vicinity of hazardous waste sites

Data were obtained regarding tin levels in air (Dannecker et al 1990 EPA 1982a 1988c NAS 1977

Sweet and Vermette 1993 WHO 1980) No monitoring data for concentrations of organotin compounds

in air were found Inorganic tin levels in water are limited to data obtained in the early 1980s (NAS 1977

WHO 1980) and more recent data were not found Due to its use in marine paints tributyltin levels as

well as di- and monobutyltin levels are monitored in water (Gomez-Ariza et al 2001 Grovhoug et al

1996 Hall 1988 Harino et al 1998 Sadiki and Williams 1996 1999 Sadiki et al 1996 Yang and

Maguire 2000) There have only a few surveys reported that monitor the occurrence of organotin

compounds in US freshwaters (Bancon-Montigny et al 2004 Jones-Lepp et al 2004) Additional

information on inorganic and organotin concentrations in all media especially air water and soil at

hazardous waste sites determined by the most sensitive analytical methods would be useful in evaluating

human exposure to tin

Several estimates concerning the human daily intake of tin have been reported (Bieacutego et al 1999 EPA

1987c Klaassen et al 1986 Krigman and Silverman 1984 WHO 1980 Ysart et al 1999) Data on the

intake of organotin compounds from food are limited (Cardwell et al 1999b Keithly et al 1999

Meacuteranger 1975 Tsuda et al 1995)

Exposure Levels in Humans Tin has been detected in human adipose tissue (Stanley 1986) urine

(Paschal et al 1998 Schramel et al 1997) and brain bone kidney liver and lung (Garciacutea et al 2001

Llobet et al 1998) Butyltin compounds have been detected in blood (Kannan et al 1999) and liver

(Kannan and Falandysz 1997 Nielsen and Strand 2002 Takahashi et al 1999) These reports are for

populations without documented high exposures to tin and tin compounds and should represent

background levels in human tissues Biological monitoring data especially for populations near

hazardous waste sites would help to assess human exposure to tin and tin compounds

This information is necessary for assessing the need to conduct health studies on these populations

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

289 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Exposures of Children Very little data were found regarding the exposure of children to tin and tin

compounds (Smart et al 1987 WHO 2003 WHOIAEA 1989) Like adults the major route of exposure

to tin will be through the diet particularly a diet high in canned foods Levels of tin and organotin

compounds in the tissue and body fluids of children have not been found Levels of tin in human breast

milk have been reported (WHOIAEA 1998) however more recent tin concentrations in human breast

milk have not been found

Child health data needs relating to susceptibility are discussed in Section 3122 Identification of Data

Needs Childrenrsquos Susceptibility

Exposure Registries No exposure registries for tin and tin compounds were located Tin and tin

compounds are not currently substances for which a sub-registry has been established in the National

Exposure Registry Tin and tin compounds will be considered in the future when chemical selection is

made for sub-registries to be established The information that is amassed in the National Exposure

Registry facilitates the epidemiological research needed to assess adverse health outcomes that may be

related to exposure to these substances

682 Ongoing Studies

The Federal Research in Progress (FEDRIP 2004) database provides additional information obtainable

from a few ongoing studies that may fill in some of the data needs identified in Section 681 These

studies are summarized in Table 6-6

The Organotin Environmental Programme (ORTEP) Association is an international non-profit

organization of producers of organotin compounds established in 1978 by companies from the United

States Europe and Japan The goals of the ORTEP Association include the promotion and

encouragement of the dissemination of scientific and technical information on the environmental effects

of organotin compounds (ORTEP 2004) The International Tin Research Institute (ITRI) tin producers

announced in October 20 2004 a project that will begin in January 2005 that will generate information

to increase the understanding of the tin industry and the applications of tin as well as the interactions of

tin with humans and the environment including increased scientific understanding of the environmental

fate of tin during its use and recycling (Tin Technology 2004)

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies

290 TIN AND TIN COMPOUNDS

6 POTENTIAL FOR HUMAN EXPOSURE

Table 6-6 Ongoing Studies on Organotin Compoundsa

Investigator Affiliation Research description Sponsor Eng G University of the

District of Columbia

Investigation of the environmental fate of triorganotins that leach in the aerobic and anaerobic sediments of DC waterways and determination of the toxicity of these compounds on the aquatic biota

Department of Agriculture

Pannell KH University of Texas at El Paso

The investigators propose to continue their initially successful study concerning the synthesis and biocidal evaluation of new organotin materials and compounds

National Institutes of Health

aFEDRIP 2004

  • 6 POTENTIAL FOR HUMAN EXPOSURE
    • 61 OVERVIEW
    • 62 RELEASES TO THE ENVIRONMENT
      • 621 Air
      • 622 Water
      • 623 Soil
        • 63 ENVIRONMENTAL FATE
          • 631 Transport and Partitioning
          • 632 Transformation and Degradation
            • 6321 Air
            • 6322 Water
            • 6323 Sediment and Soil
                • 64 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT
                  • 641 Air
                  • 642 Water
                  • 643 Sediment and Soil
                  • 644 Other Environmental Media
                    • 65 GENERAL POPULATION AND OCCUPATIONAL EXPOSURE
                    • 66 EXPOSURES OF CHILDREN
                    • 67 POPULATIONS WITH POTENTIALLY HIGH EXPOSURES
                    • 68 ADEQUACY OF THE DATABASE
                      • 681 Identification of Data Needs
                      • 682 Ongoing Studies